Use of metal hydrazide complex compounds as oxidation catalysts

ABSTRACT

The present invention relates to the use of selected metal complex compounds and ligands as oxidation catalysts as well as to a process for removing stains and soil on textiles and hard surfaces. The metal complex compounds have hydrazide ligands, preferably with electron withdrawing groups in the phenyl ring adjacent to the acyl group. Further aspects of the invention are formulations comprising such metal complex compounds, novel metal complex compounds and novel ligands.

The present invention relates to the use of selected metal complexcompounds as oxidation catalysts as well as to a process for removingstains and soil on textiles and hard surfaces. The metal complexcompounds have hydrazide ligands, preferably with electron withdrawinggroups or moieties adjacent to the acyl group. Further aspects of theinvention are formulations comprising such metal complex compounds,novel metal complex compounds and novel ligands.

Metal complex catalysts with hydrazide ligands have in generally beendescribed as oxidation catalysts, for example, in DE 196 39 603.However, the compounds disclosed are not active enough. The instantinvention solves this problem by introducing electron withdrawing groupsin the phenyl ring adjacent to the acyl group.

The instant metal complex compounds are used especially for enhancingthe action of peroxides, for example in the treatment of textilematerial, without at the same time causing any appreciable damage tofibres and dyeings. There is also no appreciable damage to fibres anddyeings if these metal complexes are used in combination with an enzymeor a mixture of enzymes.

The instant metal complex compounds may also be used as catalysts foroxidation using molecular oxygen and/or air, that is, without peroxidecompounds and/or peroxide-forming substances. The bleaching of thefabric can happen during and/or after the treatment of the fibre withthe formulation, which comprises the metal complexes.

Peroxide-containing bleaching agents have long been used in washing andcleaning processes. They have an excellent action at a liquortemperature of 90° C. and above, but their performance noticeablydecreases with lower temperatures. Various transition metal ions addedin the form of suitable salts, and coordination compounds containingsuch cations are known to activate H₂O₂. In that manner it is possiblefor the bleaching effect, which is unsatisfactory at lower temperatures,of H₂O₂ or precursors that release H₂O₂ and of other peroxo compounds,to be increased. They are important for practical purposes, in thatrespect, especially combinations of transition metal ions and ligands ofwhich the peroxide activation is manifested in an increased tendencytowards oxidation in relation to substrates and not only in acatalase-like disproportionation. The latter activation, which in thepresent case tends rather to be undesirable, could even impair thebleaching effects, which are inadequate at low temperatures, of H₂O₂ andits derivatives.

In terms of H₂O₂ activation having effective bleaching action,mononuclear and polynuclear variants of manganese complexes havingvarious ligands, especially 1,4,7-trimethyl-1,4,7-triazacyclononane andoptionally oxygen-containing bridging ligands, are currently regarded asbeing especially effective. Such catalysts are adequately stable underpractical conditions and, with Mn^(n+), contain an ecologicallyacceptable metal cation, but their use is unfortunately associated withconsiderable damage to dyes and fibres.

The aim of the present invention is accordingly to provide improvedmetal complex catalysts for oxidation processes that meet the aboverequirements and, especially, enhance the action of peroxide compoundsin the most varied fields of application without causing any appreciabledamage.

One aspect of the invention is the use, as a catalyst for oxidationreactions, of at least one complex of formula (1)[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1),wherein

-   Me is manganese, titanium, iron, cobalt, nickel or copper;-   X is a coordinating or bridging radical;-   n is an integer from 1 to 4;-   m is an integer from 0 to 2;-   p is an integer having a value of from 0 to 10;-   z is the charge of the metal complex,-   Y is a counter-ion,-   q=z/(charge of Y), and-   L is a ligand of formula (2)

wherein

-   R₁ denotes CF₃ or C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,    C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl which are substituted by    one or more electron withdrawing substituents; or-   phenyl or naphthyl which are substituted by one or more electron    withdrawing substituents;-   R₄ denotes hydrogen, C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,    C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl, or unsubstituted or    substituted heteroaryl;-   R₂ and R₃ independently of each other denote hydrogen, unsubstituted    or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,    C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl or unsubstituted or    substituted heteroaryl; or-   R₂ and R₃, together with the alkylidene carbon atom linking them,    form an unsubstituted or substituted 5-, 6-, 7-, 8- or 9-membered    ring which may contain further hetero atoms.

Under electron withdrawing substituents there are understood suchsubstituents which have a -I and/or -M effect in aromatic ring systems.

Me represents a metal selected from manganese, titanium, iron, cobalt,nickel or copper, preferably from Mn(II)-(III)-(IV)-(V),Cu(I)-(II)-(III), Fe(I)-(II)-(III)-(IV), Co(I)-(II)-(III),Ni(I)-(II)-(III), Ti(II)-(III)-(IV) and more preferably selected fromMn(II)-(III)-(IV)-(V), Cu(I)-(II)-(III), Fe(I)-(II)-(III)-(IV) andCo(I)-(II)-(III).

L represents a ligand as herein defined, or its protonated ordeprotonated analogue.

Where applicable the acyl hydrazone derivatives can be in their E- orZ-configuration.

When R₄ is hydrogen the ligand of formula (2) may be in one of itstautomeric forms or as a mixture of its different tautomeric forms.

Suitable substituents for the alkyl, heteroalkyl, cycloalkyl, alkenyl,cycloalkenyl, alkinyl, phenyl, naphthyl, aralkyl, heteroaralkyl andcycloheteroalkyl groups are especially C₁-C₄alkyl; C₁-C₄alkoxy; hydroxy;sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groupsmay be quaternised; phenyl; phenoxy or naphthyloxy; preferably hydroxyl,halogen and C₁-C₄alkoxy.

In general unsubstituted alkyl, heteroalkyl, cycloalkyl, alkenyl,cycloalkenyl, alkinyl, phenyl, naphthyl, aralkyl, heteroaralkyl andcycloheteroalkyl are preferred.

Cyclic compounds are preferably 5-, 6- or 7-membered rings, 6-memberedrings are preferred.

Aryl is phenyl or naphthyl.

The C₁-C₁₈alkyl radicals mentioned for the compounds of formula (2) are,for example, straight-chain or branched alkyl radicals, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl orstraight-chain or branched pentyl, hexyl, heptyl or octyl. Preference isgiven to C₁-C₁₂alkyl radicals, especially C₁-C₈alkyl radicals andpreferably C₁-C₄alkyl radicals. The mentioned alkyl radicals may beunsubstituted or substituted e.g. by hydroxy, C₁-C₄alkoxy, sulfo or bysulfato, especially by hydroxy. The corresponding unsubstituted alkylradicals are preferred. Very special preference is given to methyl andethyl, especially methyl.

Examples of aryl radicals that come into consideration for the compoundsof formula (2) are phenyl or naphthyl each unsubstituted or substitutedby C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxy, sulfo,hydroxy, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, wherein the amino groups may be quaternised, phenyl,phenoxy or by naphthyloxy. Preferred substituents are C₁-C₄alkyl,C₁-C₄alkoxy, phenyl and hydroxy.

Special preference is given to the corresponding phenyl radicals.

The C₁-C₆alkylene groups mentioned for the compounds of formula (2) are,for example, straight-chain or branched alkylene radicals, such asmethylene, ethylene, n-propylene or n-butylene. C₁-C₄alkylene groups arepreferred. The alkylene radicals mentioned may be unsubstituted orsubstituted, for example by hydroxy or C₁-C₄alkoxy.

In the compounds of formulae (1) and (2), halogen is preferablychlorine, bromine or fluorine, with special preference being given tochlorine.

C₃-C₁₂cycloalkyl refers to saturated cyclic hydrocarbons.C₃-C₁₂Cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyloder 2-adamantyl.

C₂-C₁₈alkenyl is for example vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl,3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl,2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl,1,4-pentadien-3-yl, or signifies different isomers of hexenyl, octenyl,nonenyl, decenyl or dodecenyl.

C₃-C₁₂ cycloalkenyl refers to unsaturated hydrocarbon residuescontaining one or multiple double bonds such, 2-cyclobuten-1-yl,2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl,2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl,2-norbornen-1-yl, 2,5-norbornadien-1-yl or7,7-dimethyl-2,4-norcaradien-3-yl.

C₇-C₉aralkyl is for example benzyl, β-phenyl-ethyl, α,α-dimethylbenzyl.

C₅-C₁₆heteroaralkyl signifies for example a C₁-C₈ alkyl moiety which issubstituted with a C₄-C₈heteroaryl group, preferably with aC₅-C₆heteroraryl group.

C₅-C₆heteroaryl is for example pyridine or pyrimidine.

X represents any coordinating or bridging species, preferably selectedfrom any mono-, bi- or tri-charged anions and any neutral molecules ableto coordinate the metal in a mono-, bi- or tri-dentate manner,preferably selected from O₂ ²⁻, O²⁻, RBO₂ ²⁻, RCOO⁻, RCONR⁻, HOO⁻, OH⁻,RO⁻, NO₃ ⁻, NO₂ ⁻, NO, CO, S²⁻, RS⁻, PO₃ ⁴⁻, STP-derived anions,PO₃OR³⁻, H₂O, CO₃ ²⁻, HCO₃ ⁻, ROH, NRR′R″, CH₃CN, RCN, Cl⁻, Br⁻, OCN⁻,SCN⁻, CN⁻, N₃ ⁻, F⁻, I⁻, RO⁻, ClO₄ ⁻, SO₄ ²⁻, HSO₄—, SO₃ ²⁻, RSO₃ ⁻,LMeO⁻ and LMeOO⁻, and more preferably selected from O₂ ²⁻, O²⁻, RBO₂ ²⁻,RCOO⁻ (preferably CH₃COO⁻), HOO⁻, OH⁻, RO⁻, NO₃ ⁻, NO₂ ⁻, NO, CO, S²⁻,RS⁻, PO₃ ⁴⁻, PO₃OR³⁻, H₂O, CO₃ ²⁻, HCO₃ ⁻, ROH, NRR′R″, CH₃CN, RCN, Cl⁻,Br⁻, OCN⁻, SCN⁻, CN⁻, N₃ ⁻, F⁻, I⁻, RO⁻, ClO₄ ⁻, SO₄ ²⁻, HSO₄—, SO₃ ²⁻,SO₃ ²⁻, RSO₃ ⁻ (preferably CF₃SO₃ ⁻), wherein R is as defined below, Land Me have the definitions and preferred meanings given herein aboveand herein below. R is especially preferably hydrogen, C₁-C₄alkyl orphenyl, especially hydrogen.

Y represents any non-coordinated counter ion, preferably selected fromRCOO⁻, ClO₄ ⁻, BF₄ ⁻, PF₆ ⁻, RSO₃ ⁻, RSO₄ ⁻, SO₄ ²⁻, S₂O₆ ⁻, OCN⁻, SCN⁻,NO₃ ⁻, NO₂ ⁻, F⁻, Cl⁻, Br⁻, I⁻, RO⁻, ClO₄ ⁻, BR₄ ⁻, FeCl₄ ⁻, RBO₂ ⁻, SO₃²⁻, HSO₄ ²⁻, N⁺RR′R″R′″, SbCl₆ ⁻, CuCl₄ ⁻, CN⁻, PO₄ ³⁻, HPO₄ ²⁻, H₂PO₄²⁻, STP-derived anions, CO₃ ²⁻, HCO₃ ⁻, Li⁺, Ba²⁺, Na⁺, Mg²⁺, K⁺, Ca²⁺,Cs⁺ and PR₄ ⁺ and more preferably selected from RCOO⁻, ClO₄ ⁻, BF₄ ⁻,PF₆ ⁻, RSO₃ ⁻, RSO₄ ⁻ (preferably CF₃SO₃ ⁻), SO₄ ²⁻, S₂O₆ ⁻, OCN⁻, SCN⁻,NO₃ ⁻, NO₂ ⁻, F⁻, Cl⁻, Br⁻, I⁻, RO⁻, ClO₄ ⁻, BR₄ ⁻, FeCl₄ ⁻, RBO₂ ⁻, SO₃²⁻, HSO₄ ²⁻, N⁺RR′R″R′″, SbCl₆ ⁻, CuCl₄ ⁻, PO₄ ³⁻, HPO₄ ²⁻, H₂PO₄ ²⁻,CO₃ ²⁻, HCO₃ ⁻, Li⁺, Ba²⁺, Na⁺, Mg²⁺, K⁺, Ca²⁺ and Cs⁺.

R, R′, R″, R′″ independently represent a group selected from hydrogen,hydroxyl, —OR₁₀ wherein R₁₀ is alkyl, alkenyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group.Preferably R, R′, R″, R′″ represent hydrogen, optionally substitutedalkyl or optionally substituted aryl, more preferably hydrogen oroptionally substituted phenyl, naphthyl or C₁₋₄-alkyl;

Y can also be a customary organic counter-ion, for example citrate,oxalate or tartrate.

The counter ions Y in formula (1) balance the charge z on the complexformed by the ligand L, metal Me and coordinating or bridging species X.Thus, if the charge z is positive, Y may be an anion such as RCOO⁻, ClO₄⁻, BF₄ ⁻, PF₆ ⁻, RSO₃ ⁻, RSO₄ ⁻ (preferably CF₃SO₃ ⁻), SO₄ ²⁻, OCN⁻,SCN⁻, NO₃ ⁻, F⁻, Cl⁻, Br⁻, I⁻, RO⁻, ClO₄ ⁻, HSO₄ ²⁻, PO₄ ³⁻, HPO₄ ²⁻,H₂PO₄ ²⁻, CO₃ ²⁻ or HCO₃ ⁻, with R being hydrogen, optionallysubstituted alkyl or optionally substituted aryl. If z is negative, Ymay be a common cation such as an alkali metal, alkaline earth metal or(alkyl)ammonium cation.

The charge of the counter-ion Y is accordingly preferably 1+, 2+, 1− or2−, especially 1+ or 1−. Particularly 1−.

For the compounds of formula (1), n is preferably an integer having avalue of from 1 to 4, preferably 1 or 2 and especially 1.

For the compounds of formula (1), m is preferably an integer having avalue of 1 or 2, especially 1.

For the compounds of formula (1), p is preferably an integer having avalue of from 0 to 4, especially 2.

For the compounds of formula (1), z is preferably an integer having avalue of from 8− to 8+, especially from 4− to 4+ and especiallypreferably from 0 to 4+. z is more especially the number 0.

For the compounds of formula (1), q is preferably an integer from 0 to8, especially from 0 to 4, and is especially preferably the number 0.

Preferably X is CH₃CN, H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂ ²⁻, O²⁻, R₂₈COO⁻,R₂₈O⁻, LMeO⁻ and LMeOO⁻; Y is R₂₈COO⁻, ClO₄ ⁻, BF₄ ⁻, PF₆ ⁻, R₂₈SO₃ ⁻,R₂₈SO₄ ⁻, SO₄ ²⁻, NO₃ ⁻, F⁻, Cl⁻, Br⁻ and I⁻;

-   R₂₈ is hydrogen, unsubstituted or substituted C₁-C₁₈alkyl or phenyl.

Preferably R₁ is —(CH₂)_(k)—N⁺(R₁₀₀R′₁₀₀R″₁₀₀)₃A⁻, wherein A⁻ is ananion and k is a number from 1 to 4; or phenyl substituted with 1 to 5electron withdrawing substituents selected from the group consisting of

-   —O—C(O)OR₁₀₀, —COOR₁₀₀, —C(O)N(R₁₀₀R′₁₀₀), —C(O)—R₁₀₀, —CN, —NO₂,    —SO₃R₁₀₀, —CF₃, F, Cl, Br, I, —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻, —N(R₁₀₁R′₁₀₁)    and

-    wherein-   R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl or    phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen atom    to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; * is the point of attachment and A⁻    is an anion, R₁₀₁, R′₁₀₁ independently are —C(O)—R₁₀₀,    —C(O)N(R₁₀₀R′₁₀₀) or —C(O)OR₁₀₀;    or-   R₁ together with the electron withdrawing substituent is a group

The anion A⁻ is preferably RCOO⁻, ClO₄ ⁻, BF₄ ⁻, PF₆ ⁻, RSO₃ ⁻, RSO₄ ⁻(preferably CF₃SO₃ ⁻), SO₄ ²⁻, OCN⁻, SCN⁻, NO₃ ⁻, F⁻, Cl⁻, Br⁻, I⁻, RO⁻,ClO₄ ⁻, HSO₄ ²⁻, PO₄ ³⁻, HPO₄ ²⁻, H₂PO₄ ²⁻, CO₃ ²⁻ or HCO₃ ⁻, with Rbeing hydrogen, unsubstituted or optionally substituted C₁-C₁₈alkyl

More preferably A⁻ is RSO₃ ⁻, OCN⁻, SCN⁻, NO₃ ⁻, F⁻, I⁻ and Cl⁻. Mostpreferably A⁻ is Cl⁻.

For example the catalyst is of formula (3) or (4)

wherein

-   Me is manganese in oxidation states II-V or iron in oxidation states    I to IV;-   X is CH₃CN, H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂ ²⁻, O²⁻, R₂₈COO⁻, R₂₈O⁻;-   R₂₈ is hydrogen, unsubstituted or substituted C₁-C₁₈alkyl or phenyl;-   p is an integer from 1 to 4;-   R₁ is —(CH₂)_(k)—N⁺(R₁₀₀R′₁₀₀R″₁₀₀)₃A⁻, wherein A⁻ is an anion and k    is a number from 1 to 4; or phenyl substituted with 1 to 5 electron    withdrawing substituents;-   R₂ denotes hydrogen, unsubstituted or substituted C₁-C₂₈alkyl,    C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl,    C₇-C₉aralkyl, C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl,    C₅-C₁₆heteroaralkyl, unsubstituted or substituted phenyl or    naphthyl, or unsubstituted or substituted heteroaryl;-   R₅, R₆, R₇ and R₈ independently from each other are hydrogen,    unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl; —OR₁₀₀,    —NR₁₀₀R′₁₀₀, halogen; or independently have the meaning as defined    for R₁; or-   R₅ and R₆, R₆ and R₇ and/or R₇ and R₈, may be linked together to    form 1, 2 or 3 carbocyclic or heterocyclic rings, which may be    uninterrupted or interrupted by one or more —O—, —S— or —NR₉— and/or    which may be further fused with other aromatic rings and/or which    may be substituted with one or more C₁-C₆alkyl groups.

In a specific embodiment of the invention the catalyst is of formula (3)or (4)

wherein

-   Me is manganese in oxidation states II-V or iron in oxidation states    I to IV;-   X is CH₃CN, H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂ ²⁻, O²⁻, R₂₈COO⁻, R₂₈O⁻;-   R₂₈ is hydrogen, unsubstituted or substituted C₁-C₁₈alkyl or phenyl;-   p is an integer from 1 to 4;-   R₁ is —(CH₂)_(k)—N⁺(R₁₀₀R′₁₀₀R″₁₀₀)₃A⁻, wherein A⁻ is an anion and k    is a number from 1 to 4; or phenyl substituted with 1 to 5 electron    withdrawing substituents selected from the group consisting of-   —OC(O)OR₁₀₀, —COOR₁₀₀, —C(O)—R₁₀₀, —CN, —NO₂, —SO₃R₁₀₀, —CF₃, F, Cl,    Br, I, —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻, —N(R₁₀₁R′₁₀₁) and

-    wherein R₁₀₀, R′₁₀₀, R″₁₀₀ are independently hydrogen, C₁-C₁₈alkyl    or phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen    atom to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; * is the point of attachment and A⁻    is an anion,-   R₁₀₁, R′₁₀₁ independently are —C(O)—R₁₀₀, —C(O)N(R₁₀₀R′₁₀₀) or    —C(O)OR₁₀₀;    or-   R₁ together with the electron withdrawing substituent is a group

-   R₂ denotes hydrogen, unsubstituted or substituted C₁-C₂₈alkyl,    C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl,    C₇-C₉aralkyl, C₃-C₂₈heteroalkyl, C₃-C₁₂cycloheteroalkyl,    C₅-C₁₆heteroaralkyl, unsubstituted or substituted phenyl or    naphthyl, or unsubstituted or substituted heteroaryl;-   R₅, R₆, R₇ and R₈ independently from each other are hydrogen,    unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl; —OR₁₀₀,    —NR₁₀₀R′₁₀₀, halogen; or independently have the meaning as defined    for R₁; or-   R₅ and R₆, R₆ and R₇ and/or R₇ and R₈, may be linked together to    form 1, 2 or 3 carbocyclic or heterocyclic rings, which may be    uninterrupted or interrupted by one or more —O—, —S— or —NR₉— and/or    which may be further fused with other aromatic rings and/or which    may be substituted with one or more C₁-C₆alkyl groups.

Examples of suitable anions A⁻ have already been given above. Mostpreferred is Cl⁻.

Particularly preferred is R₁ in the meaning of phenyl substituted with 1to 5 electron withdrawing substituents selected from the groupconsisting of

-   —OC(O)OR₁₀₀, —COOR₁₀₀, —C(O)—R₁₀₀, —CN, —NO₂, —SO₃R₁₀₀, —CF₃, F, Cl,    Br, I, —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻, —N(R₁₀₁R′₁₀₁) and

-    wherein R₁₀₀, R′₁₀₀, R″₁₀₀ are independently hydrogen, C₁-C₁₈alkyl    or phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen    atom to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; * is the point of attachment and A⁻    is an anion,-   R₁₀₁, R′₁₀₁ independently are —C(O)—R₁₀₀, —C(O)N(R₁₀₀R′₁₀₀) or    —C(O)OR₁₀₀;    or-   R₁ together with the electron withdrawing substituent is a group

In another preferred embodiment R₁ has the meaning of—(CH₂)_(k)—N⁺(CH₃)₃A⁻. Definitions for the substituents have alreadybeen given above.

The R₅-R₈ in both phenyl rings can be selected independently from thedefinitions given above and, for example, R₅ in one ring can have adifferent meaning from the R₅ in the other ring. This applies equally tothe R₆ to R₈.

Preferably Me is manganese in oxidation states II-V or iron in oxidationstates I to IV;

-   X is H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, R₂₈COO⁻ or R₂₈O⁻;-   R₂₈ is hydrogen, unsubstituted or substituted C₁-C₁₈alkyl;-   p is an integer 1 or 2;-   R₁ is phenyl substituted with 1 to 5 electron withdrawing    substituents selected from the group consisting of-   —OR₁₀₀, —COOR₁₀₀, —C(O)—R₁₀₀, —CN, —NO₂, —SO₃R₁₀₀, —CF₃, F, Cl, Br,    I, —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻, —N(R₁₀₁R′₁₀₁) or

-    wherein R₁₀₀, R′₁₀₀, R″₁₀₀ are independently hydrogen, C₁-C₁₈alkyl    or phenyl, * is the point of attachment and A⁻ is an anion;-   R₁₀₁, R′₁₀₁ independently are —C(O)—R₁₀₀, —C(O)N(R₁₀₀R′₁₀₀) or    —C(O)OR₁₀₀;-   R₂, R₅, R₆, R₇ and R₈ independently from each other are hydrogen,    unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl; —OR₁₀₀,    —NR₁₀₀R′₁₀₀, halogen; or independently have the meaning as defined    for R₁.

In a specific embodiment of the invention the integers m and p informula (I) are 0 and the ligand L of formula (2) is used as a catalystfor oxidation reactions;

wherein the substituents are as defined above including theirpreferences.

Surprisingly it has been found that the ligands alone can also be usedas catalysts for oxidation reactions for example in a washing process.

The complex compounds of formula (1) or the pure ligands of formula (2)are used as catalysts together with peroxide or a peroxide-formingsubstance, O₂ and/or air for the bleaching of stains or of soiling ontextile material in the context of a washing process or by the directapplication of a stain remover; for the cleaning of hard surfaces,especially kitchen surfaces, wall tiles or floor tiles; for the use inautomatic dishwashing compositions; for the bleaching of stains or ofsoiling on textile material by atmospheric oxygen, whereby the bleachingis catalysed during and/or after the treatment of the textile in thewashing liquor; for the prevention of redeposition of migrating dyesduring the washing of textile material; for the use in washing andcleaning solutions having an antibacterial action; as pretreatmentagents for bleaching textiles; as catalysts in selective oxidationreactions in the context of organic synthesis; for the waste watertreatment; for bleaching in the context of paper-making; forsterilization; and for contact lens disinfection.

Another aspect of the invention is a process for the bleaching of stainsor of soiling on textile materials in the context of a washing processor by the direct application of a stain remover and for the cleaning ofhard surfaces comprising

bringing into contact a textile material or hard surface material in anaqueous medium, a complex compound of formula (1) or a ligand of formula(2) as described above and a peroxide or a peroxide-forming substance orO₂ and/or air.

The ligands can be prepared according to standard procedures by reactinga carbonyl compound, such as an aldehyde with a primary amine to formthe corresponding Schiff base, in particular with a hydrazide of formula(6) with a carbonyl compound of formula (7) wherein the substituents areas defined above.

Individual ligands are summarized in the following table.

It will be appreciated that the complex (1) can be formed by anyappropriate means, including in situ formation whereby precursors of thecomplex are transformed into the active complex of general formula (1)under conditions of storage or use. Preferably, the complex is formed asa well-defined complex or in a solvent mixture comprising a salt of themetal Me and the ligand L or ligand L-generating species. Alternatively,the catalyst may be formed in situ from suitable precursors for thecomplex, for example in a solution or dispersion containing theprecursor materials. In one such example, the active catalyst may beformed in situ in a mixture comprising a salt of the metal Me and theligand L, or a ligand L-generating species, in a suitable solvent. Thus,for example, if Me is manganese, an manganese salt such as MnCl₂ orMn(OOCCH₃)₂ can be mixed in solution with the ligand L, or a ligandL-generating species, to form the active complex. Such synthesisprocedures are for example described in Inorganica Chimica Acta (1974),9(2), 137-42; Monatshefte fuer Chemie (1976), 107(6), 1455-62;Transition Metal Chemistry (Dordrecht, Netherlands) (1977), 2(1), 29-30;Inorganica Chimica Acta (2007), 360(5), 1599-1608; Malaysian Journal ofScience, 25(1), 107-114; 2006; Pestycydy (Warsaw), (1-2), 21-31; 2004 orin Journal of the Indian Chemical Society, 81(11), 950-953; 2004.

In another such example, the ligand L, or a ligand L-generating species,can be mixed with metal Me ions present in the substrate or wash liquorto form the active catalyst in situ. Suitable ligand L-generatingspecies include metal-free compounds or metal coordination complexesthat comprise the ligand L and can be substituted by metal Me ions toform the active complex according to formula (1).

The metal complex compounds of formula (1) or the ligands of formula (2)are used together as catalysts with peroxide or a peroxide-formingsubstance, O₂ and/or air. Examples that may be mentioned in that regardinclude the following uses:

-   -   a) the bleaching of stains or of soiling on textile material in        the context of a washing process or by the direct application of        a stain remover;    -   b) the cleaning of hard surfaces, especially kitchen surfaces,        wall tiles or floor tiles, for example to remove stains that        have formed as a result of the action of moulds (“mould        stains”); the use in automatic dishwashing compositions is also        a preferred use;    -   c) the bleaching of stains or of soiling on textile material by        atmospheric oxygen, whereby the bleaching is catalysed during        and/or after the treatment of the textile in the washing liquor;    -   d) the prevention of redeposition of migrating dyes during the        washing of textile material;    -   e) use in washing and cleaning solutions having an antibacterial        action;    -   f) as pretreatment agents for bleaching textiles;    -   g) as catalysts in selective oxidation reactions in the context        of organic synthesis;    -   h) waste water treatment;    -   i) use as a catalyst for reactions with peroxy compounds for        bleaching in the context of paper-making. This relates        especially to the delignification of cellulose and bleaching of        the pulp, which can be carried out in accordance with customary        procedures. Also of interest is the use as a catalyst for        reactions with peroxy compounds for the bleaching of waste        printed paper;    -   j) sterilisation and    -   k) contact lens disinfection.

Preference is given to the bleaching of stains or soiling on textilematerial; to the cleaning of hard surfaces, especially kitchen surfaces,wall tiles, floor tiles as well as the use in automatic dishwasherformulations; to the bleaching of stains or of soiling on textilematerial by atmospheric oxygen, whereby the bleaching is catalysedduring and/or after the treatment of the textile in the washing liquor;or to the prevention of redeposition of migrating dyes in the context ofa washing process.

The preferred metals for these uses are manganese and/or iron, inparticular manganese.

It should be emphasised that the use of metal complex compounds, forexample, in the bleaching of textile or hard surface material, does notcause any appreciable damage to fibres and dyeings as well as to thehard surface materials, such as table- and kitchen-ware, as well astiles.

Processes for bleaching stains in any washing liquor are usually carriedout by adding to the washing liquor (with H₂O₂ or a precursor of H₂O₂)one or more metal complex compounds of formula (1). Alternatively, it ispossible to add a detergent that already comprises one or two metalcomplex compounds. It will be understood that in such an application, aswell as in the other applications, the metal complex compounds offormula (1) can alternatively be formed in situ, the metal salt (e.g.manganese(II) salt, such as manganese(II) chloride, and/or iron(II)salt, such as iron(II) chloride) and the ligand being added in thedesired molar ratios.

Consequently a further aspect of the invention is a detergent, cleaning,disinfecting or bleaching composition comprising

-   I) from 0 to 50 wt-%, based on the total weight of the    composition, A) of at least one anionic surfactant and/or B) of a    non-ionic surfactant,-   II) from 0 to 70 wt-%, based on the total weight of the    composition, C) of at least one builder substance,-   III) from 1-99 wt-%, based on the total weight of the    composition, D) of at least one peroxide and/or one peroxide-forming    substance, O₂ and/or air,-   IV) E) at least one metal complex compound of formula (1) or a    ligand of formula (2) as defined above in an amount that, in the    liquor, gives a concentration of from 0.5 to 100 mg/liter of liquor,    when from 0.5 to 50 g/liter of the detergent, cleaning, disinfecting    or bleaching agent are added to the liquor,-   V) from 0-20 wt-%, based on the total weight of the composition, of    at least one further additive, and-   VI) water ad 100 wt-%, based on the total weight of the composition.

Preferably such a composition is used for a textile material or ahardsurface material.

All wt-% are based on the total weight of the detergent, cleaning,disinfecting or bleaching composition.

The detergent, cleaning, disinfecting or bleaching composition can beany kind of industrial or domestic cleaning, disinfecting or bleachingformulation.

It can be used for example in compositions used for textile material aswell as in composition used for hardsurfaces, such as hard surfacematerials, such as table- and kitchen-ware, as well as tiles.

Preferred hard surface cleaning compositions are dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations.

The above percentages are in each case percentage by weight, based onthe total weight of the composition. The compositions preferably containfrom 0.005 to 2 wt-% of at least one metal complex compound of formula(1), more preferably from 0.01 to 1 wt-% and most preferably from 0.05to 1 wt-%.

When the compositions according to the invention comprise a component A)and/or B), the amount thereof is preferably from 1 to 50 wt-%,especially from 1 to 30 wt-%.

When the compositions according to the invention comprise a componentC), the amount thereof is preferably from 1 to 70 wt-%, especially from1 to 50 wt-%. Special preference is given to an amount of from 5 to 50wt-% and especially an amount of from 10 to 50 wt-%.

Corresponding washing, cleaning, disinfecting or bleaching processes areusually carried out by using an aqueous liquor containing from 0.1 to200 mg of one or more compounds of formula (1) per liter of liquor. Theliquor preferably contains from 1 to 50 mg of at least one compound offormula (1) per liter of liquor.

The composition according to the invention can be, for example, aperoxide-containing heavy-duty detergent or a separate bleachingadditive, or a stain remover that is to be applied directly. A bleachingadditive is used for removing coloured stains on textiles in a separateliquor before the clothes are washed with a bleach-free detergent. Ableaching additive can also be used in a liquor together with ableach-free detergent.

Stain removers can be applied directly to the textile in question andare used especially for pretreatment in the event of heavy localsoiling.

The stain remover can be applied in liquid form, by a spraying method orin the form of a solid substance, such as a powder especially as agranule.

Granules can be prepared, for example, by first preparing an initialpowder by spray-drying an aqueous suspension comprising all thecomponents listed above except for component E), and then adding the drycomponent E) and mixing everything together. It is also possible to addcomponent E) to an aqueous suspension containing components A), B), C)and D) and then to carry out spray-drying.

It is also possible to start with an aqueous suspension that containscomponents A) and C), but none or only some of component B). Thesuspension is spray-dried, then component E) is mixed with component B)and added, and then component D) is mixed in the dry state. It is alsopossible to mix all the components together in the dry state.

The anionic surfactant A) can be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture thereof. Preference is given toalkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefinsulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or toan α-sulfonic fatty acid salt or an ester thereof.

Preferred sulfonates are, for example, alkylbenzenesulfonates havingfrom 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates havingfrom 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfateshaving from 8 to 18 carbon atoms in the alkyl radical, and fatty acidsalts derived from palm oil or tallow and having from 8 to 18 carbonatoms in the alkyl moiety. The average molar number of ethylene oxideunits added to the alkyl ether sulfates is from 1 to 20, preferably from1 to 10. The cation in the anionic surfactants is preferably an alkalinemetal cation, especially sodium or potassium, more especially sodium.Preferred carboxylates are alkali metal sarcosinates of formulaR₁₉—CON(R₂₀)CH₂COOM₁ wherein R₁₉ is C₉-C₁₇alkyl or C₉-C₁₇alkenyl, R₂₀ isC₁-C₄alkyl and M₁ is an alkali metal, especially sodium.

The non-ionic surfactant B) may be, for example, a primary or secondaryalcohol ethoxylate, especially a C₈-C₂₀ aliphatic alcohol ethoxylatedwith an average of from 1 to 20 mol of ethylene oxide per alcohol group.Preference is given to primary and secondary C₁₀-C₁₅ aliphatic alcoholsethoxylated with an average of from 1 to 10 mol of ethylene oxide peralcohol group. Non-ethoxylated non-ionic surfactants, for examplealkylpolyglycosides, glycerol monoethers and polyhydroxyamides(glucamide), may likewise be used.

The total amount of anionic and non-ionic surfactants is preferably from5 to 50 wt-%, especially from 5 to 40 wt-% and more especially from 5 to30 wt-%. The lower limit of those surfactants to which even greaterpreference is given is 10 wt-%.

In addition to anionic and/or non-ionic surfactants the composition maycontain cationic surfactants. Possible cationic surfactants include allcommon cationic surface-active compounds, especially surfactants havinga textile softening effect.

Non-limited examples of cationic surfactants are given in the formulasbelow:

wherein

-   each radical R_(α) is independent of the others C₁₋₆-alkyl-,    -alkenyl- or -hydroxyalkyl; each radical R_(β) is independent of the    others C₈₋₂₈-alkyl- or alkenyl;-   R_(γ) is R_(α) or (CH₂)_(n)-T-R_(β);-   R_(δ) is R_(α) or R_(β) or (CH₂)_(n)-T-R_(β); T=—CH₂—, —O—CO— or    —CO—O— and-   n is between 0 and 5.

Preferred cationic surfactants present in the composition according tothe invention include hydroxyalkyl-trialkyl-ammonium-compounds,especially C₁₂₋₁₈-alkyl(hydroxyethyl)dimethyl-ammonium compounds, andespecially preferred the corresponding chloride salts. Compositions ofthe present invention can contain between 0.5 wt-% and 15 wt-% of thecationic surfactant, based on the total weight of the composition.

As builder substance C) there come into consideration, for example,alkali metal phosphates, especially tripolyphosphates, carbonates andhydrogen carbonates, especially their sodium salts, silicates, aluminumsilicates, polycarboxylates, polycarboxylic acids, organic phosphonates,aminoalkylenepoly(alkylenephosphonates) and mixtures of such compounds.

Silicates that are especially suitable are sodium salts of crystallinelayered silicates of the formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20.

Among the aluminum silicates, preference is given to those commerciallyavailable under the names zeolite A, B, X and HS, and also to mixturescomprising two or more of such components. Special preference is givento zeolite A.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates, and also tocopolymers thereof with maleic anhydride. Preferred polycarboxylic acidsare nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylene-diamine disuccinate either in racemic form or in theenantiomerically pure (S,S) form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that areespecially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid anddiethylenetriaminepenta-methylenephosphonic acid, and also saltsthereof. Also preferred polyphosphonates have the following formula

wherein

-   R₁₈ is CH₂PO₃H₂ or a water soluble salt thereof and-   d is an integer of the value 0, 1, 2 or 3.

Especially preferred are the polyphosphonates wherein b is an integer ofthe value of 1.

The amount of the peroxide or the peroxide-forming substance ispreferably 0.5-30 wt-%, more preferably 1-20 wt-% and especiallypreferably 1-15 wt-%.

As the peroxide component D) there come into consideration everycompound which is capable of yielding hydrogen peroxide in aqueoussolutions, for example, the organic and inorganic peroxides known in theliterature and available commercially that bleach textile materials atconventional washing temperatures, for example at from 10 to 95° C.

Preferably, however, inorganic peroxides are used, for examplepersulfates, perborates, percarbonates and/or persilicates.

Example of suitable inorganic peroxides are sodium perboratetetrahydrate or sodium perborated monohydrate, sodium percarbonate,inorganic peroxyacid compounds, such as for example potassiummonopersulphate (MPS). If organic or inorganic peroxyacids are used asthe peroxygen compound, the amount thereof will normally be within therange of about 2-80 wt-%, preferably from 4-30 wt-%.The organic peroxides are, for example, mono- or poly-peroxides, ureaperoxides, a combination of a C₁-C₄alkanol oxidase and C₁-C₄alkanol(Such as methanol oxidase and ethanol as described in WO95/07972),alkylhydroxy peroxides, such as cumene hydroperoxide and t-butylhydroperoxide.

The peroxides may be in a variety of crystalline forms and havedifferent water contents, and they may also be used together with otherinorganic or organic compounds in order to improve their storagestability.

All these peroxy compounds may be utilized alone or in conjunction witha peroxyacid bleach precursor and/or an organic bleach catalyst notcontaining a transition metal. Generally, the bleaching composition ofthe invention can be suitably formulated to contain from 2 to 80 wt-%,preferably from 4 to 30 wt-%, of the peroxy bleaching agent.

As oxidants, peroxo acids can also be used. One example are organic monoperacids of formula

wherein

-   M signifies hydrogen or a cation,-   R₁₉ signifies unsubstituted C₁-C₁₈alkyl; substituted C₁-C₁₈alkyl;    unsubstituted aryl; substituted aryl; —(C₁-C₆alkylene)-aryl, wherein    the alkylene and/or the alkyl group may be substituted; and    phthalimidoC₁-C₈alkylene, wherein the phthalimido and/or the    alkylene group may be substituted.

Preferred mono organic peroxy acids and their salts are those of formula

wherein

-   M signifies hydrogen or an alkali metal, and-   R′₁₉ signifies unsubstituted C₁-C₄alkyl; phenyl;    —C₁-C₂alkylene-phenyl or phthalimidoC₁-C₈alkylene.

Especially preferred is CH₃COOOH and its alkali salts.

Especially preferred is also ε-phthalimido peroxy hexanoic acid and itsalkali salts.

Also suitable are diperoxyacids, for example, 1,12-diperoxydodecanedioicacid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrassilic acid,diperoxysebasic acid, diperoxyisophthalic acid,2-decyldiperoxybutane-1,4-diotic acid and 4,4′-sulphonylbisperoxybenzoicacid.

Instead of the peroxy acid it is also possible to use organic peroxyacid precursors and H₂O₂. Such precursors are the correspondingcarboxyacid or the corresponding carboxyanhydrid or the correspondingcarbonylchlorid, or amides, or esters, which can form the peroxy acidson perhydrolysis. Such reactions are commonly known.

Peroxyacid bleach precursors are known and amply described inliterature, such as in the British Patents 836988; 864,798; 907,356;1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522;EP-A-0174132; EP-A-0120591; and U.S. Pat. Nos. 1,246,339; 3,332,882;4,128,494; 4,412,934 and 4,675,393.

Peroxy acids precursers are often referred to as bleach activators.Suitable bleach activators include the bleach activators, that carry O-and/or N-acyl groups and/or unsubstituted or substituted benzoyl groups.Preference is given to polyacylated alkylenediamines, especiallytetraacetylethylenediamine (TAED); acylated glycolurils, especiallytetraacetyl glycol urea (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU);sodium-4-benzoyloxy benzene sulphonate (SBOBS);sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate;sodium-4-methyl-3-benzoloxy benzoate; trimethyl ammoniumtoluoyloxy-benzene sulphonate; acylated triazine derivatives, especially1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); compounds offormula (6):

wherein R₂₂ is a sulfonate group, a carboxylic acid group or acarboxylate group, and wherein R₂₁ is linear or branched (C₇-C₁₅)alkyl,especially activators known under the names SNOBS, SLOBS and DOBA;acylated polyhydric alcohols, especially triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran; and also acetylatedsorbitol and mannitol and acylated sugar derivatives, especiallypentaacetylglucose (PAG), sucrose polyacetate (SUPA),pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone. It isalso possible to use the combinations of conventional bleach activatorsknown from German Patent Application DE-A-44 43 177. Nitrile compoundsthat form perimine acids with peroxides also come into consideration asbleach activators.

Another useful class of peroxyacid bleach precursors is that of thecationic i.e. quaternary ammonium substituted peroxyacid precursors asdisclosed in U.S. Pat. Nos. 4,751,015 and 4,397,757, in EP-A0284292 andEP-A-331,229. Examples of peroxyacid bleach precursors of this classare: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonatechloride-(SPCC), N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammoniumchloride- (ODC), 3-(N,N,N-trimethyl ammonium) propylsodium-4-sulphophenyl carboxylate and N,N,N-trimethyl ammoniumtoluoyloxy benzene sulphonate.

A further special class of bleach precursors is formed by the cationicnitriles as disclosed in EP-A-303,520, WO 96/40661 and in EuropeanPatent Specification No.'s 458,396, 790244 and 464,880. These cationicnitriles also known as nitril quats have the formula

wherein

-   R₃₀ is a C₁-C₂₄alkyl; a C₁-C₂₄alkenyl; an alkaryl having a    C₁-C₂₄alkyl; a substituted C₁-C₂₄alkyl; a substituted C₁-C₂₄alkenyl;    a substituted aryl,-   R₃₁ and R₃₂ are each independently a C₁-C₃alkyl; hydroxyalkyl having    1 to 3 carbon atoms, —(C₂H₄O)_(n)H, n being 1 to 6; —CH₂—CN-   R₃₃ is a C₁-C₂₀alkyl; a C₁-C₂₀alkenyl; a substituted C₁-C₂₀alkyl; a    substituted C₁-C₂₀alkenyl; an alkaryl having a C₁-C₂₄alkyl and at    least one other substituent,-   R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ are each independently hydrogen, a    C₁-C₁₀alkyl, a C₁-C₁₀alkenyl, a substituted C₁-C₁₀alkyl, a    substituted C₁-C₁₀alkenyl, carboxyl, sulfonyl or cyano-   R₃₈, R₃₉, R₄₀ and R₄₁ are each independently a C₁-C₆alkyl,-   n′ is an integer from 1 to 3,-   n″ is an integer from 1 to 16, and-   X is an anion.

Other nitril quats have the following formula

wherein

-   R₄₂ and R₄₃ form, together with the nitrogen atom to which they are    bonded, a ring comprising 4 to 6 carbon atoms, this ring may also be    substituted by C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₅-alkanoyl, phenyl,    amino, ammonium, cyano, cyanamino or chloro and 1 or 2 carbon    atom(s) of this ring may also be substituted by a nitrogen atom, by    a oxygen atom, by a N—R₄₇-group and/or by a R₄₄—N—R₄₇-group, wherein    R₄₇ is hydrogen, C₁-C₅-alkyl, C₂-C₅-alkenyl, C₂-C₅-alkinyl, phenyl,    C₇-C₉-aralkyl, C₅-C₇-cycloalkyl, C₁-C₅-alkanoyl, cyanomethyl or    cyano,-   R₄₄ is C₁-C₂₄—, preferably C₁-C₄-alkyl; C₂-C₂₄-alkenyl, preferably    C₂-C₄-alkenyl, cyanomethyl or C₁-C₄-alkoxy-C₁-C₄-alkyl,-   R₄₅ and R₄₆ are independently from each other hydrogen; C₁-C₄-alkyl;    C₁-C₄-alkenyl; C₁-C₄-alkoxy-C₁-C₄-alkyl; phenyl or    C₁-C₃-alkylphenyl, preferably hydrogen, methyl or phenyl, whereby    preferably the moiety R₄₅ signifies hydrogen, if R₄₆ is not    hydrogen, and-   X⁻ is an anion.

Suitable examples of nitril quats of formula (ε) are

Other nitrile quats have the formula

wherein

-   A is a saturated ring formed by a plurality of atoms in addition to    the N₁ atom, the saturated ring atoms to include at least one carbon    atom and at least one heteroatom in addition to the N₁ atom, the    said one heteroatom selected from the group consisting of O, S and N    atoms, the substituent R₄₇ bound to the N₁ atom of the Formula (φ)    structure is (a) a C₁-C₈-alkyl or alkoxylated alkyl where the alkoxy    is C₂₋₄, (b) a C₄-C₂₄cycloalkyl, (c) a C₇-C₂₄alkaryl, (d) a    repeating or nonrepeating alkoxy or alkoxylated alcohol, where the    alkoxy unit is C₂₋₄, or (e) —CR₅₀R₅₁—C≡N where R₅₀ and R₅₁ are each    H, a C₁-C₂₄alkyl, cycloalkyl, or alkaryl, or a repeating or    nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is    C₂₋₄, in Formula (φ) at least one of the R₄₈ and R₄₉ substituents is    H and the other of R₄₈ and R₄₉ is H, a C₁-C₂₄alkyl, cycloalkyl, or    alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated    alcohol where the alkoxy unit is C₂₋₄, and Y is at least one    counterion.

In a preferred embodiment of the invention the catalyst of formula (1)is used together with a peroxide or peroxide precursor and a bleachactivator which is selected from the group consisting oftetraacetylethylenediamine, pentaacetylglucose, sodiumoctanoyloxybenzene-sulfonate, sodium nonanoyloxybenzenesulfonate, sodiumdecanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate,sodium dodecanoyloxybenzenesulfonate, octanoyl-oxybenzoic acid,nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoicacid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene,decanoyl-oxybenzene, undecanoyloxybenzene and dodecanoyloxybenzene.

The precursors may be used in an amount of up to 12 wt-%, preferablyfrom 2-10 wt-% based on the total weight of the composition.

It is also possible to use further bleach catalysts, which are commonlyknown, for example transition metal complexes as disclosed in EP1194514, EP 1383857 or WO04/007657. Further bleach catalysts aredisclosed in: US2001044401, EP0458397, WO9606154, EP1038946, EP0900264,EP0909809, EP1001009, WO9965905, WO0248301, WO0060045, WO02077145,WO0185717, WO0164826, EP0923635, DE 19639603, DE102007017654,DE102007017657, DE102007017656, US20030060388, EP0918840B1, EP1174491A2,EP0805794B1, WO9707192A1, U.S. Pat. No. 6,235,695B1, EP0912690B1,EP832969B1, U.S. Pat. No. 6,479,450B1, WO9933947A1, WO0032731A1,WO03054128A1, DE102004003710, EP1083730, EP1148117, EP1445305, U.S. Pat.No. 6,476,996, EP0877078, EP0869171, EP0783035, EP0761809 and EP1520910.

It is possible to use H₂O₂, O₂, air, the peroxy-containing compounds,the peroxy-acids as well as their precursors, further bleach catalystand bleach activists in any combination with the inventive metalcomplexes.

The compositions may comprise, in addition to the combination accordingto the invention, one or more optical brighteners, for example from theclasses bis-triazinylamino-stilbenedisulfonic acid,bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl orbis-benzofuranylbiphenyl, α bis-benzoxalyl derivative,bis-benzimidazolyl derivative or coumarin derivative or a pyrazolinederivative.

The compositions may furthermore comprise one or more further additives.Such additives are, for example, dirt-suspending agents, for examplesodium carboxymethylcellulose; pH regulators, for example alkali metalor alkaline earth metal silicates; foam regulators, for example soap;salts for adjusting the spray drying and the granulating properties, forexample sodium sulfate; perfumes; and also, if appropriate, antistaticsand softening agents such as, for example, smectite; bleaching agents;pigments; and/or toning agents. These constituents should especially bestable to any bleaching agent employed.

If the detergent composition is used in an automatic dishwasher it isalso common to use silver-corrosion inhibitors.

Such auxiliaries are added in a total amount of from 0.1-20 wt-%,preferably from 0.5-10 wt-%, especially from 0.5-5 wt-%, based on thetotal weight of the detergent formulation.

Furthermore, the detergent may optionally also comprise enzymes. Enzymescan be added for the purpose of stain removal. The enzymes usuallyimprove the action on stains caused by protein or starch, such as, forexample, blood, milk, grass or fruit juices. Preferred enzymes arecellulases and proteases, especially proteases. Cellulases are enzymesthat react with cellulose and its derivatives and hydrolyse them to formglucose, cellobiose and cellooligosaccharides. Cellulases remove dirtand, in addition, have the effect of enhancing the soft handle of thefabric.

Examples of customary enzymes include, but are by no means limited to,the following

-   proteases as described in U.S. Pat. No. 6,242,405, column 14, lines    21 to 32;-   lipases as described in U.S. Pat. No. 6,242,405, column 14, lines 33    to 46;-   amylases as described in U.S. Pat. No. 6,242,405, column 14, lines    47 to 56; and-   cellulases as described in U.S. Pat. No. 6,242,405, column 14, lines    57 to 64.    Commercially available detergent proteases, such as Alcalase®,    Esperase®, Everlase®, Savinase®, Kannase® and Durazym®, are sold    e.g. by NOVOZYMES A/S.    Commercially available detergent amylases, such as Termamyl®,    Duramyl®, Stainzyme®, Natelase®, Ban® and Fungamyl®, are sold e.g.    by NOVOZYMES A/S.    Commercially available detergent ellulases, such as Celluzyme®,    Carezyme® and Endolase®, are sold e.g. by NOVOZYMES A/S.    Commercially available detergent lipases, such as Lipolase®,    Lipolase Ultra® and Lipoprime®, are sold e.g. by NOVOZYMES A/S.    Suitable mannanases, such as Mannanaway®, are sold by NOVOZYMES A/S.

Beside in laundry care products, in a hard surface cleaner, especiallyin a composition used in automatic dishwashers the following enzymes arealso commonly used: proteases, amylases, pullulanases, cutinases andlipases, for example proteases such as BLAP®, Optimase®, Opticlean®,Maxacal®, Maxapem®, Esperase® and/or Savinase®, amylases such asTermamyl®, Amylase-LT®, Maxamyl® and/or Duramyl®, lipases such asLipolase®, Lipomax®, Lumafast® and/or Lipozym®. The enzymes which may beused can, as described e.g. in International Patent Applications WO92/11347 and WO 94/23005, be adsorbed on carriers and/or embedded inencapsulating substances in order to safeguard them against prematureinactivation. They are present in the cleaning formulations according tothe invention preferably in amounts not exceeding 5 wt-%, especially inamounts of from 0.1 wt-% to 1.2 wt-%.

Amylases: The present invention preferably makes use of amylases havingimproved stability in detergents, especially improved oxidativestability. Such amylases are non-limitingly illustrated by thefollowing: (a) An amylase according to WO 94/02597, Novo Nordisk A/S,published Feb. 3, 1994, as further illustrated by a mutant in whichsubstitution is made, using alanine or threonine (preferably threonine),of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TERMAMYL®, or the homologousposition variation of a similar parent amylase, such as B.amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)Stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th American Chemical Society National Meeting, Mar. 13-17, 1994, byC. Mitchinson. Therein it was noted that bleaches in automaticdishwashing detergents inactivate alpha-amylases but that improvedoxidative stability amylases have been made by Genencor from B.lichenifonnis NCIB8061. Any other oxidative stability-enhanced amylasecan be used.Proteases: Protease enzymes are usually present in preferred embodimentsof the invention at levels between 0.001 wt-% and 5 wt-%. Theproteolytic enzyme can be of animal, vegetable or microorganism(preferred) origin. More preferred is serine proteolytic enzyme ofbacterial origin. Purified or nonpurified forms of enzyme may be used.Proteolytic enzymes produced by chemically or genetically modifiedmutants are included by definition, as are close structural enzymevariants. Suitable commercial proteolytic enzymes include Alcalase®,Esperase®, Durazyme®, Savinase®, Maxatase®, Maxacal®, and Maxapem® 15(protein engineered Maxacal). Purafect® and subtilisin BPN and BPN′ arealso commercially available.

When present, lipases comprise from about 0.001 wt-% to about 0.01 wt-%of the instant compositions and are optionally combined with from about1 wt-% to about 5 wt-% of a surfactant having limesoap-dispersingproperties, such as an alkyldimethylamine N-oxide or a sulfobetaine.Suitable lipases for use herein include those of bacterial, animal andfungal origin, including those from chemically or genetically modifiedmutants.

When incorporating lipases into the instant compositions, theirstability and effectiveness may in certain instances be enhanced bycombining them with small amounts (e.g., less than 0.5 wt-% of thecomposition) of oily but non-hydrolyzing materials.

The enzymes, when used, may be present in a total amount of from 0.01 to5 wt-%, especially from 0.05 to 5 wt-% and more especially from 0.1 to 4wt-%, based on the total weight of the detergent formulation.

If the detergent formulation is a hard surface cleaning composition,preferably a dishwashing detergent formulation, more preferably anautomatic dishwashing detergent formulation, then it can optionally alsocomprises from about 0.001 wt-% to about 10 wt-%, preferably from about0.005 wt-% to about 8 wt-%, most preferably from about 0.01 wt-% toabout 6 wt-% of an enzyme stabilizing system. The enzyme stabilizingsystem can be any stabilizing system which is compatible with thedetersive enzyme. Such a system may be inherently provided by otherformulation actives, or be added separately, e.g., by the formulator orby a manufacturer of detergent-ready enzymes. Such stabilizing systemscan, for example, comprise calcium ion, boric acid, propylene glycol,short chain carboxylic acids, boronic acids, and mixtures thereof, andare designed to address different stabilization problems depending onthe type and physical form of the detergent composition.

In order to enhance the bleaching action, the compositions may, inaddition to comprising the catalysts described herein, also comprisephotocatalysts the action of which is based on the generation of singletoxygen.

Further preferred additives to the compositions according to theinvention are dye-fixing agents and/or polymers which, during thewashing of textiles, prevent staining caused by dyes in the washingliquor that have been released from the textiles under the washingconditions. Such polymers are preferably polyvinylpyrrolidones,polyvinylimidazoles or polyvinylpyridine-N-oxides, which may have beenmodified by the incorporation of anionic or cationic substituents,especially those having a molecular weight in the range of from 5000 to60 000, more especially from 10 000 to 50 000. Such polymers are usuallyused in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5wt-%, more especially from 0.1 to 2 wt-%, based on the total weight ofthe detergent formulation. Preferred polymers are those mentioned inWO-A-02/02865 (see especially page 1, last paragraph and page 2, firstparagraph) and those in WO-A-04/05688.

When the inventive detergent composition is used as hardsurface cleaner,especially when the composition is used in automatic dishwasherformulation then, it has been found out, that it is preferable to avoidthe use of simple calcium-precipitating soaps as antifoams in thepresent compositions as they tend to deposit on the dishware. Indeed,phosphate esters are not entirely free of such problems and theformulator will generally choose to minimize the content of potentiallydepositing antifoams in the instant compositions.

Other examples for foam suppressors are paraffin, paraffin/alcoholcombinations, or bisfatty acid amides.

The hard surface cleaning compositions, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations herein may also optionally contain one or more heavy metalchelating agents, such as hydroxyethyldiphosphonate (HEDP). Moregenerally, chelating agents suitable for use herein can be selected fromthe group consisting of amino carboxylates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof. Other suitable chelating agents for use herein are thecommercial DEQUEST series, and chelants from Nalco, Inc.

Aminocarboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts thereof and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates).

Further biodegradable sequestrants are, for example, aminoacid acetates,such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginicacid derivatives, such as Baypure CX.

Preferably, the aminophosphonates do not contain alkyl or alkenyl groupswith more than about 6 carbon atoms.

A highly preferred biodegradable chelator for use herein isethylenediamine disuccinate (“EDDS”).

If utilized, these chelating agents or transition-metal selectivesequestrants will generally comprise from about 0.001 wt-% to about 10wt-%, more preferably from about 0.05 wt-% to about 1 wt-% of the hardsurface cleaning compositions, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations herein.

Preferred hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations herein may additionally contain a dispersant polymer. Whenpresent, a dispersant polymer is typically at levels in the range from 0wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 20 wt-%,more preferably from about 1 wt-% to about 8 wt-% of the detergentcomposition. Dispersant polymers are useful for improved filmingperformance of the present dishwasher detergent compositions, especiallyin higher pH embodiments, such as those in which wash pH exceeds about9.5. Particularly preferred are polymers, which inhibit the depositionof calcium carbonate or magnesium silicate on dishware.

Suitable polymers are preferably at least partially neutralized oralkali metal, ammonium or substituted ammonium (e.g., mono-, di- ortriethanolammonium) salts of polycarboxylic acids. The alkali metal,especially sodium salts are most preferred. While the molecular weightof the polymer can vary over a wide range, it preferably is from about1,000 to about 500,000, more preferably is from about 1,000 to about250,000.

Unsaturated monomeric acids that can be polymerized to form suitabledispersant polymers include acrylic acid, maleic acid (or maleicanhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid,citraconic acid and methylenemalonic acid. The presence of monomericsegments containing no carboxylate radicals such as methyl vinyl ether,styrene, ethylene, etc. is suitable provided that such segments do notconstitute more than about 50 wt-% of the dispersant polymer.

Copolymers of acrylamide and acrylate having a molecular weight of fromabout 3,000 to about 100,000, preferably from about 4,000 to about20,000, and an acrylamide content of less than about 50 wt-%, preferablyless than about 20 wt-% of the dispersant polymer can also be used. Mostpreferably, such dispersant polymer has a molecular weight of from about4,000 to about 20,000 and an acrylamide content of from about 0 wt-% toabout 15 wt-%, based on the total weight of the polymer.

Particularly preferred dispersant polymers are low molecular weightmodified polyacrylate copolymers. Such copolymers contain as monomerunits: a) from about 90 wt-% to about 10 wt-%, preferably from about 80wt-% to about 20 wt-% acrylic acid or its salts and b) from about 10wt-% to about 90 wt-%, preferably from about 20 wt-% to about 80 wt-% ofa substituted acrylic monomer or its salt and have the general formula:

—[(C(R_(a))C(R_(b))(C(O)OR_(c))] wherein the apparently unfilledvalencies are in fact occupied by hydrogen and at least one of thesubstituents R_(a), R_(b), or R_(c), preferably R_(a) or R_(b), is a 1to 4 carbon alkyl or hydroxyalkyl group; R_(a) or R_(b) can be ahydrogen and R_(c) can be a hydrogen or alkali metal salt. Mostpreferred is a substituted acrylic monomer wherein R_(a) is methyl,R_(b) is hydrogen, and R_(c) is sodium.

A suitable low molecular weight polyacrylate dispersant polymerpreferably has a molecular weight of less than about 15,000, preferablyfrom about 500 to about 10,000, most preferably from about 1,000 toabout 5,000. The most preferred polyacrylate copolymer for use hereinhas a molecular weight of about 3,500 and is the fully neutralized formof the polymer comprising about 70 wt-% acrylic acid and about 30 wt-%methacrylic acid.

Other dispersant polymers useful herein include the polyethylene glycolsand polypropylene glycols having a molecular weight of from about 950 toabout 30,000.

Yet other dispersant polymers useful herein include the cellulosesulfate esters such as cellulose acetate sulfate, cellulose sulfate,hydroxyethyl cellulose sulfate, methylcellulose sulfate, andhydroxypropylcellulose sulfate. Sodium cellulose sulfate is the mostpreferred polymer of this group.

Other suitable dispersant polymers are the carboxylated polysaccharides,particularly starches, celluloses and alginates.

Yet another group of acceptable dispersants are the organic dispersantpolymers, such as polyaspartate.

Depending on whether a greater or lesser degree of compactness isrequired, filler materials can also be present in the instant hardsurface cleaning compositions, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations. These include sucrose, sucrose esters, sodium sulfate,potassium sulfate, etc., in amounts up to about 70 wt-%, preferably from0 wt-% to about 40 wt-% of the hard surface cleaning compositions,preferably dishwashing detergent formulations, more preferably automaticdishwashing detergent formulations. Preferred filler is sodium sulfate,especially in good grades having at most low levels of trace impurities.

Sodium sulfate used herein preferably has a purity sufficient to ensureit is non-reactive with bleach; it may also be treated with low levelsof sequestrants, such as phosphonates or EDDS in magnesium-salt form.Note that preferences, in terms of purity sufficient to avoiddecomposing bleach, applies also to pH-adjusting component ingredients,specifically including any silicates used herein.

Organic solvents that can be used in the cleaning formulations accordingto the invention, especially when the latter are in liquid or pasteform, include alcohols having from 1 to 4 carbon atoms, especiallymethanol, ethanol, isopropanol and tert-butanol, diols having from 2 to4 carbon atoms, especially ethylene glycol and propylene glycol, andmixtures thereof, and the ethers derivable from the mentioned classes ofcompound. Such water-miscible solvents are present in the cleaningformulations according to the invention preferably in amounts notexceeding 20 wt-%, especially in amounts of from 1 wt-% to 15 wt-%.

Many hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations herein will be buffered, i.e., they are relativelyresistant to pH drop in the presence of acidic soils. However, othercompositions herein may have exceptionally low buffering capacity, ormay be substantially unbuffered. Techniques for controlling or varyingpH at recommended usage levels more generally include the use of notonly buffers, but also additional alkalis, acids, pH-jump systems, dualcompartment containers, etc., and are well known to those skilled in theart. Certain hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations, comprise a pH-adjusting component selected fromwater-soluble alkaline inorganic salts and water-soluble organic orinorganic builders. The pH-adjusting components are selected so thatwhen the hard surface cleaning composition, preferably dishwashingdetergent formulation, more preferably automatic dishwashing detergentformulation is dissolved in water at a concentration of 1,000-5,000 ppm,the pH remains in the range of above about 8, preferably from about 9.5to about 11. The preferred nonphosphate pH-adjusting component can beselected from the group consisting of:

-   (i) sodium carbonate or sesquicarbonate;-   (ii) sodium silicate, preferably hydrous sodium silicate having    SiO₂:Na₂O ratio of from about 1:1 to about 2:1, and mixtures thereof    with limited quantities of sodium metasilicate;-   (iii) sodium citrate;-   (iv) citric acid;-   (v) sodium bicarbonate;-   (vi) sodium borate, preferably borax;-   (vii) sodium hydroxide; and-   (viii) mixtures of (i)-(vii).

Preferred embodiments contain low levels of silicate (i.e. from about 3wt-% to about 10 wt-% SiO₂).

Illustrative of highly preferred pH-adjusting component systems of thisspecialized type are binary mixtures of granular sodium citrate withanhydrous sodium carbonate, and three-component mixtures of granularsodium citrate trihydrate, citric acid monohydrate and anhydrous sodiumcarbonate.The amount of the pH adjusting component in compositions used forautomatic dishwashing is preferably from about 1 wt-% to about 50 wt-%of the composition. In a preferred embodiment, the pH-adjustingcomponent is present in the composition in an amount from about 5 wt-%to about 40 wt-%, preferably from about 10 wt-% to about 30 wt-%.For compositions herein having a pH between about 9.5 and about 11 ofthe initial wash solution, particularly preferred automatic dishwashingdetergent formulations embodiments comprise, by weight of the automaticdishwashing detergent formulations, from about 5 wt-% to about 40 wt-%,preferably from about 10 wt-% to about 30 wt-%, most preferably fromabout 15 wt-% to about 20 wt-%, of sodium citrate with from about 5 wt-%to about 30 wt-%, preferably from about 7 wt-% to 25 wt-%, mostpreferably from about 8 wt-% to about 20 wt-% sodium carbonate.The essential pH-adjusting system can be complemented (i.e. for improvedsequestration in hard water) by other optional detergency builder saltsselected from nonphosphate detergency builders known in the art, whichinclude the various water-soluble, alkali metal, ammonium or substitutedammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates.Preferred are the alkali metals, especially sodium, salts of suchmaterials. Alternate water-soluble, non-phosphorus organic builders canbe used for their sequestering properties. Examples of polyacetate andpolycarboxylate builders are the sodium, potassium, lithium, ammoniumand substituted ammonium salts of ethylenediamine tetraacetic acid;nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinicacid, oxydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid,and sodium benzene polycarboxylate salts.

The detergent formulations can take a variety of physical forms such as,for example, powder granules, tablets (tabs), gel and liquid. Examplesthereof include, inter alia, conventional high-performance detergentpowders, supercompact high-performance detergent powders and tabs. Oneimportant physical form is the so-called concentrated granular form,which is added to a washing machine.

Also of importance are so-called compact or supercompact detergents. Inthe field of detergent manufacture, there is a trend towards theproduction of such detergents that contain an increased amount of activesubstances. In order to minimize energy consumption during the washingprocedure, compact or supercompact detergents need to act effectively atlow washing temperatures, for example below 40° C., or even at roomtemperature (25° C.). Such detergents usually contain only small amountsof fillers or of substances, such as sodium sulfate or sodium chloride,required for detergent manufacture. The total amount of such substancesis usually from 0 to 10 wt-%, especially from 0 to 5 wt-%, moreespecially from 0 to 1 wt-%, based on the total weight of the detergentformulation. Such (super)compact detergents usually have a bulk densityof from 650 to 1000 g/l, especially from 700 to 1000 g/l and moreespecially from 750 to 1000 g/l.

The detergent formulations can also be in the form of tablets (tabs).The advantages of tabs reside in the ease of dispensing and conveniencein handling. Tabs are the most compact form of solid detergentformulation and usually have a volumetric density of, for example, from0.9 to 1.3 kg/liter. To achieve rapid dissolution, such tabs generallycontain special dissolution aids:

-   -   carbonate/hydrogen carbonate/citric acid as effervescents;    -   disintegrators, such as cellulose, carboxymethyl cellulose or        cross-linked poly(N-vinyl-pyrrolidone);    -   rapidly dissolving materials, such as sodium (potassium)        acetates, or sodium (potassium) citrates;    -   rapidly dissolving, water-soluble, rigid coating agents, such as        dicarboxylic acids.        The tabs may also comprise combinations of such dissolution        aids.

The detergent formulation may also be in the form of an aqueous liquidcontaining from 5 wt-% to 50 wt-%, preferably from 10 wt-% to 35 wt-%,of water or in the form of a non-aqueous liquid containing no more than5 wt-%, preferably from 0 wt-% to 1 wt-% of water. Non-aqueous liquiddetergent formulations may comprise other solvents as carriers. Lowmolecular weight primary or secondary alcohols, for example methanol,ethanol, propanol and isopropanol, are suitable for that purpose. Thesolubilising surfactant used is preferably a monohydroxy alcohol butpolyols, such as those containing from 2 to 6 carbon atoms and from 2 to6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerol and1,2-propanediol) can also be used. Such carriers are usually used in atotal amount of from 5 wt-% to 90 wt-%, preferably from 10 wt-% to 50wt-%, based on the total weight of the detergent formulation. Thedetergent formulations can also used in so-called “unit liquid dose”form.

Also an aspect of the invention is a granule comprising

-   a) from 1-99 wt-%, based on the total weight of the granule, of at    least one metal complex compound of formula (1) or a ligand of    formula (2) as defined above and of at least one peroxide,-   b) from 1-99 wt-%, based on the total weight of the granule, of at    least one binder,-   c) from 0-20 wt-%, based on the total weight of the granule, of at    least one encapsulating material,-   d) from 0-20 wt-%, based on the total weight of the granule, of at    least one further additive and-   e) from 0-20 wt-% based on the total weight of the granule, of    water.

All wt-% are based on the total weight of the granule.

As binder (b) there come into consideration water-soluble, dispersibleor water-emulsifiable anionic dispersants, non-ionic dispersants,polymers and waxes.

The anionic dispersants used are, for example, commercially availablewater-soluble anionic dispersants for dyes, pigments etc.

The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated diphenyls or diphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acid,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalenemethanesulfonates, lignosulfonates or oxylignosulfonatesand heterocyclic polysulfonic acids.

Especially suitable anionic dispersants are condensation products ofnaphthalenesulfonic acids with formaldehyde, sodium salts of polymerisedorganic sulfonic acids, (mono-/di-)-alkylnaphthalenesulfonates,polyalkylated polynuclear arylsulfonates, sodium salts of polymerisedalkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates andcondensation products of naphthalenesulfonic acid with apolychloromethyldiphenyl.

Suitable non-ionic dispersants are especially compounds having a meltingpoint of, preferably, at least 35° C. that are emulsifiable, dispersibleor soluble in water, for example the following compounds:

-   1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl    alcohol;-   2. addition products of, preferably, from 2 to 80 mol of alkylene    oxide, especially ethylene oxide, wherein some of the ethylene oxide    units may have been replaced by substituted epoxides, such as    styrene oxide and/or propylene oxide, with higher unsaturated or    saturated monoalcohols, fatty acids, fatty amines or fatty amides    having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl    phenols, benzyl phenols or alkyl phenols, the alkyl radicals of    which have at least 4 carbon atoms;-   3. alkylene oxide, especially propylene oxide, condensation products    (block polymers);-   4. ethylene oxide/propylene oxide adducts with diamines, especially    ethylenediamine;-   5. reaction products of a fatty acid having from 8 to 22 carbon    atoms and a primary or secondary amine having at least one    hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene    oxide addition products of such hydroxyalkyl-group-containing    reaction products;-   6. sorbitan esters, preferably having long-chain ester groups, or    ethoxylated sorbitan esters, such as polyoxyethylene sorbitan    monolaurate having from 4 to 10 ethylene oxide units or    polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene    oxide units;-   7. addition products of propylene oxide with a tri- to hexa-hydric    aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or    pentaerythritol; and-   8. fatty alcohol polyglycol mixed ethers, especially addition    products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol    of propylene oxide with aliphatic monoalcohols having from 8 to 22    carbon atoms.    Especially suitable non-ionic dispersants are surfactants of formula    R₂₃—O-(alkylene-O)_(n)—R₂₄  (11),    wherein-   R₂₃ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl;-   R₂₄ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at    least 6 carbon atoms; or benzyl;-   “alkylene” is an alkylene radical having from 2 to 4 carbon atoms    and-   n is a number from 1 to 60.

The substituents R₂₃ and R₂₄ in formula (11) are advantageously each thehydrocarbon radical of an unsaturated or, preferably, saturatedaliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbonradical may be straight-chain or branched. R₂₃ and R₂₄ are preferablyeach independently of the other an alkyl radical having from 9 to 14carbon atoms. Aliphatic saturated monoalcohols that come intoconsideration include natural alcohols, e.g. lauryl alcohol, myristylalcohol, cetyl alcohol or stearyl alcohol, and also synthetic alcohols,e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononylalcohol, trimethylhexanol, trimethylnonyl alcohol, decanol,C₉-C₁₁oxo-alcohol, tridecyl alcohol, isotridecyl alcohol and linearprimary alcohols (Alfols) having from 8 to 22 carbon atoms. Someexamples of such Alfols are Alfol (8-10), Alfol (9-11), Alfol (10-14),Alfol (12-13) and Alfol (16-18). (“Alfol” is a registered trade mark ofthe company Sasol Limited). Unsaturated aliphatic monoalcohols are, forexample, dodecenyl alcohol, hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present singly or in the form of mixtures oftwo or more components, e.g. mixtures of alkyl and/or alkenyl groupsthat are derived from soybean fatty acids, palm kernel fatty acids ortallow oils.

(Alkylene-O) chains are preferably bivalent radicals of the formulae

Examples of a cycloaliphatic radical include cycloheptyl, cyclooctyl andpreferably cyclohexyl.

As non-ionic dispersants there come into consideration preferablysurfactants of formula

wherein

-   R₂₅ is C₈-C₂₂alkyl;-   R₂₆ is hydrogen or C₁-C₄alkyl;-   Y₁, Y₂, Y₃ and Y₄ are each independently of the others hydrogen,    methyl or ethyl;-   n₂ is a number from 0 to 8; and-   n₃ is a number from 2 to 40.

Further important non-ionic dispersants correspond to formula

wherein

-   R₂₇ is C₉-C₁₄alkyl;-   R₂₈ is C₁-C₄alkyl;-   Y₅, Y₆, Y₇ and Y₈ are each independently of the others hydrogen,    methyl or ethyl, one of the radicals Y₅, Y₆ and one of the radicals    Y₇, Y₈ always being hydrogen; and-   n₄ and n₅ are each independently of the other an integer from 4 to    8.

The non-ionic dispersants of formulae (11) to (13) can be used in theform of mixtures. For example, as surfactant mixtures there come intoconsideration non-end-group-terminated fatty alcohol ethoxylates offormula (7), e.g. compounds of formula (11) wherein

-   R₂₃ is C₈-C₂₂alkyl,-   R₂₄ is hydrogen and-   the alkylene-O chain is the radical —(CH₂—CH₂—O)—-   and also end-group-terminated fatty alcohol ethoxylates of formula    (9).

Examples of non-ionic dispersants of formulae (11), (12) and (13)include reaction products of a C₁₀—C₁₃fatty alcohol, e.g. aC₁₃oxo-alcohol, with from 3 to 10 mol of ethylene oxide, propylene oxideand/or butylene oxide and the reaction product of one mol of a C₁₃fattyalcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, itbeing possible for the addition products each to be end-group-terminatedwith C₁-C₄alkyl, preferably methyl or butyl.

Such dispersants can be used singly or in the form of mixtures of two ormore dispersants. Instead of, or in addition to, the anionic ornon-ionic dispersant, the granules according to the invention maycomprise a water-soluble organic polymer as binder. Such polymers may beused singly or in the form of mixtures of two or more polymers.

Water-soluble polymers that come into consideration are, for example,polyethylene glycols, copolymers of ethylene oxide with propylene oxide,gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones,vinylpyrrolidones, vinyl acetates, polyvinylimidazoles,polyvinylpyridine-N-oxides, copolymers of vinylpyrrolidone withlong-chain α-olefins, copolymers of vinyl-pyrrolidone withvinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates),copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides,copolymers of vinyl-pyrrolidone/dimethylaminopropyl acrylamides,quaternised copolymers of vinylpyrrolidones and dimethylaminoethylmethacrylates, terpolymers ofvinylcaprolactam/vinylpyrrolidone/di-methylaminoethyl methacrylates,copolymers of vinylpyrrolidone andmethacrylamidopropyl-trimethylammonium chloride, terpolymers ofcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose,polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate,copolymers of ethyl acrylate with methacrylate and methacrylic acid,copolymers of maleic acid with unsaturated hydrocarbons, and also mixedpolymerisation products of the mentioned polymers.

Of those organic polymers, special preference is given to polyethyleneglycols, carboxy-methyl cellulose, polyacrylamides, polyvinyl alcohols,polyvinylpyrrolidones, gelatin, hydro-lysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, copolymers of ethyl acrylate with methacrylate andmethacrylic acid, and polymathacrylates.

Suitable water-emulsifiable or water-dispersible binders also includeparaffin waxes.

Encapsulating materials (c) include especially water-soluble andwater-dispersible polymers and waxes. Of those materials, preference isgiven to polyethylene glycols, polyamides, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate withmethacrylate and methacrylic acid, and polymethacrylates.

Further additives (d) that come into consideration are, for example,wetting agents, dust removers, water-insoluble or water-soluble dyes orpigments, and also dissolution accelerators, optical brighteners andsequestering agents.

The preparation of the granules according to the invention is carriedout, for example, starting from:

-   a) a solution or suspension with a subsequent drying/shaping step or-   b) a suspension of the active ingredient in a melt with subsequent    shaping and solidification.

a) First of all the anionic or non-ionic dispersant and/or the polymerand, optionally, the further additives are dissolved in water andstirred, if desired with heating, until a homogeneous solution isobtained. The catalyst according to the invention is then dissolved orsuspended in the resulting aqueous solution. The solids content of thesolution should preferably be at least 30 wt-%, especially from 40 wt-%to 50 wt-%, based on the total weight of the solution. The viscosity ofthe solution is preferably less than 200 mPas.

The aqueous solution so prepared, comprising the catalyst according tothe invention, is then subjected to a drying step in which all water,with the exception of a residual amount, is removed, solid particles(granules) being formed at the same time. Known methods are suitable forproducing the granules from the aqueous solution. In principle, bothcontinuous methods and discontinuous methods are suitable. Continuousmethods are preferred, especially spray-drying and fluidised bedgranulation processes.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is effected e.g. using unitary or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-drying processmay be combined with an additional agglomeration of the liquid particleswith solid nuclei in a fluidised bed that forms an integral part of thechamber (so-called fluid spray). The fine particles (<100 μm) obtainedby a conventional spray-drying process may, if necessary after beingseparated from the exhaust gas flow, be fed as nuclei, without furthertreatment, directly into the atomizing cone of the atomiser of thespray-dryer for the purpose of agglomeration with the liquid droplets ofthe active ingredient.

During the granulation step, the water can rapidly be removed from thesolutions comprising the catalyst according to the invention, binder andfurther additives. It is expressly intended that agglomeration of thedroplets forming in the atomising cone, or agglomeration of dropletswith solid particles, will take place.

b) The catalyst according to the invention is dried in a separate stepprior to the melt-granulation and, if necessary, dry-ground in a mill sothat all the solids particles are <50 μm in size. The drying is carriedout in an apparatus customary for the purpose, for example, in a paddledryer, vacuum cabinet or freeze-dryer.

Other product forms of the present invention include product formsspecifically developed for industrial and institutional cleaning, forexample liquid solutions of the catalyst in water or organic solvents orsolid forms such as powders or granules which can be dosed in a separatebleaching step of the cleaning application.

Some of the ligands defined above are novel and are also a subject ofthe present invention.

A compound of formula (2)

wherein

-   R₁ is —(CH₂)_(k)—N⁺(R₁₀₀R′₁₀₀R″₁₀₀)₃A⁻, wherein A⁻ is an anion and k    is a number from 1 to 4; or phenyl substituted with 1 to 5 electron    withdrawing substituents —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻ wherein the-   R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl or    phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen atom    to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; and A⁻ is an anion, or-   R₁ together with the electron withdrawing substituent is a group

* is the point of attachment;

-   R₄ denotes hydrogen, C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,    C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl, or unsubstituted or    substituted heteroaryl;-   R₂ and R₃ independently of each other denote hydrogen, unsubstituted    or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,    C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl, or unsubstituted or    substituted heteroaryl; or-   R₂ and R₃, together with the alkylidene carbon atom linking them,    form an unsubstituted or substituted ring 5-, 6-, 7-, 8- or    9-membered ring which may contain further hetero atoms.

Preferred is a compound of formula (2)

wherein

-   R₁ is phenyl substituted with 1 to 5 electron withdrawing    substituents —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻ wherein the-   R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl or    phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen atom    to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; and A⁻ is an anion, or-   R₁ together with the electron withdrawing substituent is a group

* is the point of attachment;

-   R₄ denotes hydrogen, C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,    C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl, or unsubstituted or    substituted heteroaryl;-   R₂ and R₃ independently of each other denote hydrogen, unsubstituted    or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,    C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl, or unsubstituted or    substituted heteroaryl; or-   R₂ and R₃, together with the alkylidene carbon atom linking them,    form an unsubstituted or substituted ring 5-, 6-, 7-, 8- or    9-membered ring which may contain further hetero atoms.

For example a compound which is of formula (5)

wherein

-   R₁ is phenyl substituted with 1 to 5 electron withdrawing    substituents —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻ wherein the-   R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl or    phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen atom    to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; and A⁻ is an anion, or-   R₁ together with the electron withdrawing substituent is a group

* is the point of attachment;

-   R₂ denotes hydrogen, unsubstituted or substituted C₁-C₂₈alkyl,    C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl,    C₇-C₉aralkyl, C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl,    C₅-C₁₆heteroaralkyl, unsubstituted or substituted aryl, or    unsubstituted or substituted heteroaryl;-   R₅, R₆, R₇ and R₈ independently from each other are hydrogen,    unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl; —OR₁₀₀,    —NR₁₀₀R′₁₀₀, halogen or a group

-    or independently have the meaning as defined for R₁;-   or-   R₅ and R₆, R₆ and R₇ or R₇ and R₈, are linked together to form 1, 2,    3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted    or interrupted by one or more —O—, —S— or —NR₉— and/or which may be    further fused with other aromatic rings and/or which may be    substituted with one or more C₁-C₆alkyl groups.

Preferred is a compound wherein

-   R₁ is phenyl substituted with 1 to 5 electron withdrawing    substituents —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻ wherein the-   R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl or    phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen atom    to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; and A⁻ is F⁻, Cl⁻, Br⁻ or I⁻, or-   R₁ together with the electron withdrawing substituent is a group

* is the point of attachment;

-   R₂ denotes hydrogen, unsubstituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl,    C₇-C₉phenylalkyl, C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl halogen;-   R₅, R₆, R₇ and R₈ independently from each other are hydrogen,    unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl;-   or —OR₁₀₀, —NHR₁₀₀, —NR₁₀₀R′₁₀₀, halogen;-   or phenyl substituted with 1 to 5 electron withdrawing groups    selected from the group consisting of —OC(O)OR₁₀₀, —COOR₁₀₀,    —C(O)—R₁₀₀, —CN, —NO₂, —SO₃R₁₀₀, —CF₃, F, Cl, Br, I, —OR₁₀₀,    —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺ A⁻ and

-    wherein R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl    or phenyl, * is the point of attachment and A⁻ is as defined above;    or-   R₅, R₆, R₇ and R₈ together with the electron withdrawing substituent    are independently a group

Preferably R₁ is phenyl substituted with 1 to 3 electron withdrawingsubstituents —N(R₁₀₀)₃ ⁺A⁻, more preferably with 1 or 2 and mostpreferably with 1.

Yet a further aspect of the invention is a complex compound of formula(3a) or (4a)

wherein

-   Me is manganese in oxidation states II-V or iron in oxidation states    I to IV;-   X is CH₃CN, H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂ ²⁻, O²⁻, R₂₈COO⁻, R₂₈O⁻;-   R₂₈ is hydrogen, unsubstituted or substituted C₁-C₁₈alkyl or phenyl;-   p is an integer from 1 to 4;-   R₁ is —(CH₂)_(k)—N⁺(R₁₀₀R′₁₀₀R″₁₀₀)₃A⁻, wherein A⁻ is an anion and k    is a number from 1 to 4; or phenyl substituted with 1 to 5 electron    withdrawing substituents —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻ wherein the-   R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl or    phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen atom    to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; and A⁻ is F⁻, Cl⁻, Br⁻ or I, or-   R₁ together with the electron withdrawing substituent is a group

* is the point of attachment;

-   R₂ denotes hydrogen, unsubstituted or substituted C₁-C₂₈alkyl,    C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl,    C₇-C₉aralkyl, C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl,-   C₅-C₁₆heteroaralkyl, unsubstituted or substituted aryl, or    unsubstituted or substituted heteroaryl;-   R₅, R₆, R₇ and R₈ independently from each other are hydrogen,    unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl; —OR₁₀₀,    —NR₁₀₀R′₁₀₀, halogen or a group

-    or independently have the meaning as defined for R₁;    or-   R₅ and R₆, R₆ and R₇ or R₇ and R₈, are linked together to form 1, 2,    3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted    or interrupted by one or more —O—, —S— or —NR₉— and/or which may be    further fused with other aromatic rings and/or which may be    substituted with one or more C₁-C₆alkyl groups.

Yet a further aspect of the invention is a complex compound of formula(3a) or (4a)

wherein

-   Me is manganese in oxidation states II-V or iron in oxidation states    I to IV;-   X is CH₃CN, H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂ ²⁻, O²⁻, R₂₈COO⁻, R₂₈O⁻;-   R₂₈ is hydrogen, unsubstituted or substituted C₁-C₁₈alkyl or phenyl;-   p is an integer from 1 to 4;-   R₁ is phenyl substituted with 1 to 5 electron withdrawing    substituents —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺ A⁻ wherein the-   R₁₀₀, R′₁₀₀, R″₁₀₀ independently are hydrogen, C₁-C₁₈alkyl or    phenyl, or two of R₁₀₀, R′₁₀₀, R″₁₀₀ together with the nitrogen atom    to which they are bonded form a 5 or 6 membered-ring which may    contain a further nitrogen atom; and A⁻ is F⁻, Cl⁻, Br⁻ or I, or-   R₁ together with the electron withdrawing substituent is a group

* is the point of attachment;

-   R₂ denotes hydrogen, unsubstituted or substituted C₁-C₂₈alkyl,    C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl,    C₇-C₉aralkyl, C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl,    C₅-C₁₆heteroaralkyl, unsubstituted or substituted aryl, or    unsubstituted or substituted heteroaryl;-   R₅, R₆, R₇ and R₈ independently from each other are hydrogen,    unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl,    C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl,    C₃-C₂₀heteroalkyl, C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl,    unsubstituted or substituted phenyl or naphthyl; —OR₁₀₀,    —NR₁₀₀R′₁₀₀, halogen or a group

-    or independently have the meaning as defined for R₁;    or-   R₅ and R₆, R₆ and R₇ or R₇ and R₈, are linked together to form 1, 2,    3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted    or interrupted by one or more —O—, —S— or —NR₉— and/or which may be    further fused with other aromatic rings and/or which may be    substituted with one or more C₁-C₅alkyl groups.

All definitions and preferences given above apply where applicableequally to all aspects of the invention.

The following examples illustrate the invention.

Parts and percentages relate to weight, unless otherwise indicated.Temperatures are in degrees Celsius, unless otherwise indicated.

SYNTHESIS EXAMPLE 1 Preparation of

A mixture of 3.48 g of 4-chlorobenzhydrazide and 2.47 g ofsalicylaldehyde in 80 mL of ethanol is heated to 50° C. After stirringfor 30 minutes at this temperature 1 mL of concentrated hydrochloricacid is added. The resulting pale yellow suspension is stirred for 16hours, then filtrated and the residue washed with minor amounts ofethanol. After drying at 60° C. in the vacuum 4.18 g of the desiredproduct as a pale beige powder is obtained. Melting point: 223° C.

SYNTHESIS EXAMPLE 2 Preparation of

1.15 g of 3-chlorobenzhydrazide are suspended in 35 mL of ethanol andstirred at room temperature for 10 minutes. After addition of 0.93 g ofsalicylaldehyde and 1 mL of concentrated hydrochloric acid the resultingyellow solution is stirred for 16 hours at room temperature. A colorlessprecipitate is filtrated off, washed with 10 mL of water and dried at100° C. in the vacuum yielding 1.39 g of the desired product as acolorless powder. Melting point: 201.8° C.

SYNTHESIS EXAMPLE 3 Preparation of

To a mixture of 0.44 g of 4-chlorobenzhydrazide and 0.39 g of2-hydroxy-4-methoxy-benzaldehyde in 35 mL of ethanol is added 0.5 mL ofconcentrated hydrochloric acid. Immediately a yellow suspension isformed which is stirred at room temperature for 16 hours. Afterfiltrating off a pale yellow powder which is washed with 5 mL of ethanoland dried at 70° C. in vacuum 0.60 g of the desired product areobtained. Melting point: 196.9° C.

SYNTHESIS EXAMPLE 4 Preparation of

To a mixture of 0.44 g of 4-chlorobenzhydrazide and 0.39 g of2,4-dihydroxy-benzaldehyde in 35 mL of ethanol is added 0.5 mL ofconcentrated hydrochloric acid. Immediately a reddish brown solution isformed which is stirred at room temperature for 16 hours. Afterfiltrating off a beige powder which is washed with 5 mL of water anddried at 70° C. in vacuum 0.17 g of the desired product are obtained.Melting point: 280° C.

SYNTHESIS EXAMPLE 5 Preparation of

To a mixture of 0.44 g of 4-chlorobenzhydrazide in 35 mL of ethanol 0.49g of 4-diethylamino-2-hydroxy-benzaldehyde is added dropwise. After theaddition of 0.5 mL of concentrated hydrochloric acid a brown solution isformed which is stirred at room temperature for 16 hours. A brownishprecipitate is filtered off, washed with 5 mL of water and dried at 70°C. in vacuum yielding 0.70 g of the desired product are obtained.Melting point: 210° C.

SYNTHESIS EXAMPLE 6 Preparation of

To a mixture of 0.44 g of 3-chlorobenzhydrazide in 35 mL of ethanol 0.39g of 2-hydroxy-4-methoxy-benzaldehyde is added dropwise. After additionof 0.5 mL of concentrated hydrochloric acid a yellow solution is formedwhich is stirred at room temperature for 16 hours. A pale yellowprecipitate is then filtered off, which is washed with 5 mL of water anddried at 70° C. in vacuum yielding 0.38 g of the desired product.Melting point: 181.3° C.

SYNTHESIS EXAMPLE 7 Preparation of

To a mixture of 0.52 g of 4-trifluoromethyl-benzhydrazide in 15 mLethanol 0.31 g of salicyl aldehyde is added dropwise at roomtemperature. Immediately a colorless suspension is formed. Afteraddition of 0.5 mL of concentrated hydrochloric acid the suspension isstirred for 16 hours at room temperature. The precipitate is thenfiltrated off, washed with 5 mL of ethanol and dried in the vacuum at50° C. yielding 0.20 g of the desired product as a colorless powder.Melting point: 230.6° C.

SYNTHESIS EXAMPLE 8 Preparation of

To a mixture of 0.52 g of 4-trifluoromethyl-benzhydrazide in 15 mLethanol 0.39 g of 2-hydroxy-4-methoxy-benzaldehyde is added dropwise atroom temperature. After addition of 0.5 mL of concentrated hydrochloricacid a yellow suspension is formed which is stirred for 16 hours at roomtemperature. The precipitate is then filtrated off, washed with 5 mL ofethanol and dried in the vacuum at 50° C. yielding 0.51 g of the desiredproduct as a yellow powder. Melting point: 200° C. (underdecomposition).

SYNTHESIS EXAMPLE 9 Preparation of

To a mixture of 0.39 g of(4-hydrazinocarbonyl-phenyl)-trimethyl-ammonium iodide in 35 mL ofethanol 0.19 g of 2-hydroxy-4-methoxy-benzaldehyde is added dropwise atroom temperature under formation of a colorless suspension. Afteraddition of 0.5 mL of concentrated hydrochloric acid a yellow suspensionis formed which is stirred for 16 hours at room temperature. Theprecipitate is then filtrated off, washed with 5 mL of water and driedin the vacuum at 70° C. yielding 0.17 g of the desired product as acolorless powder. Melting point: 176.8° C.

SYNTHESIS EXAMPLE 10 Preparation of

To a mixture of 0.39 g of(4-hydrazinocarbonyl-phenyl)-trimethyl-ammonium iodide in 35 mL ofethanol 0.15 g of salicylaldehyde is added dropwise at room temperatureunder formation of a colorless suspension. After addition of 0.5 mL ofconcentrated hydrochloric acid stirring is continued for 16 hours atroom temperature. A colorless precipitate is then filtrated off anddried in the vacuum at 70° C. yielding 0.21 g of the desired product asa colorless powder. Melting point: 170.4° C.

SYNTHESIS EXAMPLE 11 Preparation of

0.46 g of 3-nitrobenzhydrazide are stirred for 10 min. in 35 mL ofethanol. Then 0.39 g of 2-hydroxy-4-methoxy-benzaldehyde are addeddropwise at room temperature. After addition of 0.5 mL of concentratedhydrochloric acid immediately a precipitate is formed. The yellowsuspension is stirred for 16 hours at room temperature. The precipitateis then filtrated off, washed with 5 mL of water and dried in the vacuumat 100° C. yielding 0.68 g of the desired product as a yellow solid.Melting point: 253.7° C.

SYNTHESIS EXAMPLE 12 Preparation of:

1.39 g of 3-nitrobenzhydrazide are stirred for 30 min. in 35 mL ofethanol. Then 0.93 g of salicyl aldehyde are added dropwise at roomtemperature. After addition of 1 mL of concentrated hydrochloric acid ayellow suspension is formed. The yellow suspension is stirred for 16hours at room temperature. The precipitate is then filtrated off, washedwith 10 mL of water and dried in the vacuum at 100° C. yielding 2.00 gof the desired product as a yellowish powder. Melting point: 243.7° C.

SYNTHESIS EXAMPLE 13 Preparation of

0.46 g of 4-nitrobenzhydrazide are stirred for 10 minutes in 35 mL ofethanol resulting in a yellowish suspension. Then 0.39 g of2-hydroxy-4-methoxy-benzaldehyde are added dropwise at room temperature.After addition of 0.5 mL of concentrated hydrochloric acid the yellowsuspension is stirred for 16 hours at room temperature. The precipitateis then filtrated off, washed with 5 mL of water and dried in the vacuumat 100° C. yielding 0.70 g of the desired product as a dark yellowpowder. Melting point: 214.8° C.

SYNTHESIS EXAMPLE 14 Preparation of

A mixture of 1.21 g of 4-fluorobenzhydrazide and 0.95 g ofsalicylaldehyde in 40 mL of ethanol is heated to 60° C. After additionof 5 drops of concentrated acetic acid the mixture is stirred for 1 hourat refluxing temperature. After cooling down to room temperature acolorless precipitate is filtered off and dried at 60° C. in the vacuumyielding 0.97 g of the desired product as a colorless powder.

SYNTHESIS EXAMPLE 15 Preparation of

0.99 g of 3-fluorobenzhydrazide are dissolved in 30 mL of ethanol bystirring and heating. After addition of 0.78 g of salicylaldehyde and 5drops of concentrated acetic acid the resulting yellowish solution isstirred for 1 hour at refluxing temperature. A colorless precipitate isfiltrated off, washed with water and dried at 60° C. in the vacuumyielding 1.01 g of the desired product as a colorless powder.

SYNTHESIS EXAMPLE 16 Preparation of

330 mg of 3-dimethylbenzhydrazide are dissolved in 6 mL of ethanol bystirring. After addition of 225 mg of salicylaldehyde and 0.5 mL ofconcentrated hydrochloric acid the resulting yellowish suspension isstirred for 4 hours at room temperature. The precipitate is thenfiltrated off and recrystallised from methanol. After drying in thevacuum at 25° C., 98 mg of the desired product are isolated as a yellowpowder. Melting point: 192.6° C.

SYNTHESIS EXAMPLE 17 Preparation of

134 mg of (3-hydrazinocarbonyl-phenyl)-trimethyl-ammonium iodide arestirred for 10 minutes in 8 mL of ethanol. Then 315 mg of2-hydroxy-4-methyl-benzaldehyde are added at room temperature. Afteraddition of 0.5 mL of concentrated hydrochloric acid the resultingyellowish suspension is stirred for 0.5 hours at room temperature. Theprecipitate is then filtrated off and dried in the vacuum at 25° C.,yielding 285 mg of the desired product as a yellow powder. Meltingpoint: 185.7° C.

SYNTHESIS EXAMPLE 18 Preparation of

To a mixture of 248 mg of(3-hydrazinocarbonyl-phenyl)-trimethyl-ammonium iodide in 7.5 mL ofethanol 121 mg of 4-chloro-2-hydroxybenzaldehyde are added at roomtemperature under formation of a colorless suspension. After addition of0.5 mL of concentrated hydrochloric acid stirring is continued for 16hours at room temperature. A yellow precipitate is then filtrated offand recrystallised from ethanol. After drying in the vacuum at 25° C.,90 mg of the desired product are isolated as a yellow powder.

SYNTHESIS EXAMPLE 19 Preparation of

61 mg of 4-(4-hydrazinocarbonyl-phenyl)-1,1-dimethyl-piperazin-1-iumiodide are stirred for 10 minutes in 5 mL of ethanol. Then 20 mg ofsalicylaldehyde are added at room temperature. After addition of 0.5 mLconcentrated hydrochloric acid the resulting orange suspension isstirred for 16 hours at room temperature. The precipitate is thenfiltrated off and dried in the vacuum at 25° C., yielding 26 mg of thedesired product as an orange powder.

SYNTHESIS EXAMPLE 20 Preparation of

250 mg of hydrazinocarbonylmethyl-trimethyl-ammonium iodide aresuspended in 2.5 mL of ethanol by stirring. After addition of 118 mg ofsalicylaldehyde and 0.25 mL of concentrated hydrochloric acid theresulting yellowish suspension is stirred for 16 hours at roomtemperature. The precipitate is then filtrated off and washed withethanol. After drying in the vacuum at 25° C., 270 mg of the desiredproduct are isolated as a yellow powder.

SYNTHESIS EXAMPLE 21 Preparation of

To a solution of 0.755 g of(4-hydrazinocarbonyl-phenyl)-trimethyl-ammonium iodide in 9 mL ofethanol 0.245 mL of salicylaldehyde is added dropwise at roomtemperature. After addition of 0.5 mL of concentrated hydrochloric acidstirring is continued for 16 hours at room temperature. A colorlessprecipitate is then filtrated off and dried in the vacuum at 30° C. Thisiodide salt was solved in water and passed over a DOWEX 1×8 packedcolumn. The combined water eluates were evaporated in vacuum to obtain abeige solid in 20% yield.

APPLICATION EXAMPLES Application Example 1 Peroxide Bleaching of Morinin Solution

2.5 μM catalyst solution (1:1 complex of Mn(II) chloride tetrahydratewith the ligand in question in water or methanol) are added at time t=0to a solution of 160 μM morin in 10 mM carbonate buffer, pH 10containing 10 mmol/l hydrogen peroxide. The solution is located in athermostatically controllable vessel, equipped with a magnetic stirrer,at 23° C. The extinction of the solution is measured at 410 nm over aperiod of 10 min. The values for the decoloration after 3 min. areindicated as percentages.

The following ligands were used:

TABLE 1 Ligand Extent of the decoloration after 3 min (%) L10 80 L9 85L8 77 L1 81 L7 85 L3 80 L4 46 L6 84 L5 29 L11 82 L13 83 L2 84 Referencewithout catalyst 3

The bleaching action of the compounds according to the invention is byfar superior to the reference of 10 mM hydrogen peroxide alone.

Application Example 2 Peroxide Bleaching Action in Washing Agents

7.5 g of white cotton fabric and 2.5 g of tea-stained cotton fabric aretreated in 80 ml of washing liquor. The liquor contains a standardwashing agent (ECE, 456 IEC) in a concentration of 7.5 g/l. The hydrogenperoxide concentration is 8.6 mmol/l. The catalyst concentration (1:1complex of manganese(II) chloride tetrahydrate with the ligand inquestion, prepared in methanolic solution with the addition of a smallamount of lithium hydroxide) is 50 μmol/l. The washing process iscarried out in a steel beaker in a LINITEST apparatus for 30 minutes at40° C. For evaluating the bleaching results, the increase in thelightness DY (difference in lightness according to CIE) of the stainsbrought about by the treatment is determined spectrophotometrically indifference to values obtained without the addition of a catalyst. Avalue >0 indicates catalytic activity.

TABLE 2 1:1 Mn complex with DY increase on ligand top of peroxide L105.6 L9 6.0 L8 5.9 L1 5.2 L7 2.3 L3 3.9 L4 3.2 L13 4 L6 5.9 L5 3.8 L113.6 L1 3.7 L12 3

As can be seen from Table 2 above, the manganese complexes exhibit avery good bleaching action.

The results of Table 2 show, that those manganese complexes with ligandsbearing an electron attracting group exhibit enhanced bleachingperformance.

Application Example 3 with Un-Complexed Ligands Peroxide BleachingAction in Washing Agents

22.4 g of white cotton fabric and 0.8 g of BC01 tea-stained or EMPA114red wine-stained cotton fabric are treated in 150 ml of washing liquor.The liquor contains a commercial color care washing powder in aconcentration of 4.5 g/l, and 0.83 g/l sodium percarbonate (SPC). Thecatalyst concentration ligand L10 in an un-complexed form is 20 μmol/l.The washing process is carried out in a steel beaker in a LINITESTapparatus for 40 minutes at 30° C. For evaluating the bleaching results,the increase in the lightness DY (difference in lightness according toCIE) of the stains brought about by the treatment is determinedspectrophotometrically. The higher the ΔY value, the better the bleachperformance

TABLE 3 ΔY of Acylhydrazone Ligand with SPC containing detergent BC01EMPA114 Percarbonate 6.2 21.0 alone Percarbonate + 10.4 26.8 L10

As can be seen from Table 3 above, the Ligand L10 alone exhibits a verygood bleaching action.

Application Example 4 with Un-Complexed Ligands Bleach Activity on Topof TAED Action in Washing Agents

22.4 g of white cotton fabric and 0.8 g of BC01 tea-stained or EMPA114red wine-stained cotton fabric are treated in 150 ml of washing liquor.The liquor contains a commercial color care washing powder in aconcentration of 4.5 g/l, 0.83 g/l sodium percarbonate (SPC) and 0.166 gTetraacetyethylenediamin (TAED). The catalyst concentration Ligand L10in a un-complexed form is 20 μmol/l. The washing process is carried outin a steel beaker in a LINITEST apparatus for 40 minutes at 30° C. Forevaluating the bleaching results, the increase in the lightness DY(difference in lightness according to CIE) of the stains brought aboutby the treatment is determined spectrophotometrically. The higher the ΔYvalue, the better the bleach performance

TABLE 4 ΔY of Acylhydrazone Ligand with SPC/TAED containing detergentBC01 EMPA114 SPC/TAED 9.1 24.9 SPC/TAED + L10 15.1 30.0

As can be seen from Table 4 above, the Ligand L10 exhibits a very goodbleaching action, even on top of a SPC/TAED bleach system.

Application Example 5 Un-Complexed Ligand Bleach Activity with AATCCStandard Detergent

22.4 g of white cotton fabric and 0.8 g of BC01 tea-stained cottonfabric are treated in 150 ml of washing liquor. The liquor containsAATCC standard powder detergent in a concentration of 7.5 g/l, 0.68 g/lsodium percarbonate (SPC) and 0.151 g Tetraacetyethylenediamin (TAED).The catalyst concentration Ligand L9 in a un-complexed form is 20μmol/l. The washing process is carried out in a steel beaker in aLINITEST apparatus for 40 minutes at 40° C. For evaluating the bleachingresults, the increase in the lightness DY (difference in lightnessaccording to CIE) of the stains brought about by the treatment isdetermined spectrophotometrically. The higher the ΔY value, the betterthe bleach performance

TABLE 5 ΔY of Acylhydrazone Ligand with AATCC detergent BC01 SPC/TAED12.7 SPC + L9 14.8

As can be seen from Table 5 above, the ligand L9 exhibits a very goodbleaching action, which exceeds the performance of the standard bleachsystem SPC/TAED.

Application Example 6 Un-Complexed Ligand Bleach Activity with LiquidBleach Additive

48 g of white cotton fabric and 0.8 g of BC01 tea-stained and 0.8 gEMPA114 red wine or 0.8 g BC03 tea and BC06 strawberry-stained cottonfabric are treated in 250 ml of washing liquor. The liquor contains acommercial color care washing powder in a concentration of 4.5 g/l, 2.4g/l of a commercial liquid bleach additive (Vanish). The catalystconcentration Ligand L10 in a un-complexed form is 10 μmol/l and 20μmol/l. The washing process is carried out in a steel beaker in aLINITEST apparatus for 40 minutes at 40° C. For evaluating the bleachingresults, the increase in the lightness DY (difference in lightnessaccording to CIE) of the stains brought about by the treatment isdetermined spectrophotometrically. The higher the ΔY value, the betterthe bleach performance.

TABLE 6 Acylhydrazone ligand with detergent and bleach additive BC01EMPA114 BC03 BC06 Detergent 2.7 16.3 1.9 0.1 Detergent + Bleach 6.2 22.45.1 4.9 additive Detergent + Bleach 8.1 23.2 8.4 5.9 additive + 10μmol/l L10 Detergent + Bleach 10.4 26.7 12.8 8.7 additive + 20 μmol/lL10

As can be seen from Table 6 above, the ligand L10 exhibits a very goodbleaching action also with liquid bleach additives.

Application Example 7 Un-Complexed Ligand Incorporation of L10 intoLiquid Bleach Additive

3.02 mmol/l of L10 (counter ion Cl⁻) are incorporated into a commercialliquid bleach additive. This additive is applied in a bleach experimentimmediately, 1 day, one week and one month after preparation, storage ofthe bleach additive at ambient temperature.

The washing process is as follows:

24.2 g of white cotton fabric and 0.8 g of BC01 tea-stained cottonfabric are treated in 150 ml of washing liquor. The liquor contains acommercial color care washing powder in a concentration of 4.5 g/l, 3.7g/l of the commercial liquid bleach additive containing the catalystconcentration Ligand L10 (counter ion Cl⁻) in a un-complexed form. Thewashing process is carried out in a steel beaker in a LINITEST apparatusfor 40 minutes at 40° C. For evaluating the bleaching results, theincrease in the lightness DY (difference in lightness according to CIE)of the stains brought about by the treatment is determinedspectrophotometrically. The higher the ΔY value, the better the bleachperformance.

TABLE 7 L10 containing liq. bleach additive, performance after storage(ΔY BC01) immediately 1 day 1 week 1 month L10-Bleach 10.4 10.4 10.810.1 additive

The application of the bleach additive without L10 leads to a ΔY of 6.5

The results in Table 7 indicate no loss in bleach activity after astorage time of one month.

Additionally the content of hydrogen peroxide in the bleach additive isdetermined iodometrically

TABLE 8 concentration of hydrogen peroxide (mol/l) in L10 containingbleach additive after storage immediately 1 day 1 week 1 month L10Bleach 1.93 1.93 1.92 1.92 additive

Table 8 indicates that no peroxide is decomposed in the presence of L10.

Application Example 8 Un-Complexed Ligand Dishwashing

Tee-stained cups are prepared according to the IKW method(“IKW-Arbeitskreis Maschinenspülmittel, Methoden zur Bestimmung derReinigungsleistung von maschinellen Geschirrspülmitteln (Part A and B)”,SÖFW, 11+14, 1998). Tea-stained cups are filled with a carbonate buffersolution (pH 9.6) containing 44 mM hydrogen peroxide and 30 μM catalyst.After 15 minutes the solution is removed, and the cups are rinsed withwater. The removal of the tea deposit is evaluated visually on a scalefrom 0 (i.e. unchanged, very strong deposit) to 10 (i.e. no deposit). Arating of 4.5 is observed in experiments without catalyst.

TABLE 9 Catalyst (Ligand) Rating Reference 4.5 Ligand 10 8 Ligand 121 ofSynthesis Example 21 7

The invention claimed is:
 1. A detergent, cleaning, disinfecting orbleaching composition comprising I) from 1 to 50 wt-%, wt-%, based onthe total weight of the composition, of A) at least one anionicsurfactant and/or B) a non-ionic surfactant, II) from 0 to 70 wt-%,based on the total weight of the composition, of C) at least one buildersubstance, III) from 1-99 wt-%, based on the total weight of thecomposition, of D) at least one peroxide and/or one peroxide-formingsubstance, O₂ and/or air, IV) E) at least one a compound of formula (2)as defined below in an amount that, in a liquor, gives a concentrationof from 0.5 to 100 mg/liter of liquor, when from 0.5 to 50 g/liter ofthe detergent, cleaning, disinfecting or bleaching composition are addedto the liquor, V) from 0-20 wt-%, based on the total weight of thecomposition, of at least one further additive, and VI) water ad 100wt-%, based on the total weight of the composition,

wherein R₁ denotes CF₃ or C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl, C₃-C₂₀heteroalkyl orC₃-C₁₂cycloheteroalkyl which are substituted by one or more electronwithdrawing substituents; or phenyl or naphthyl which are substituted byone or more electron withdrawing substituents; R₄ denotes hydrogen,C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl,C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl, C₃-C₂₀heteroalkyl,C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroarylalkyl, unsubstituted orsubstituted phenyl or naphthyl or unsubstituted or substitutedheteroaryl; and R₂ and R₃ independently of each other denote hydrogen,unsubstituted or substituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl,C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl, C₃-C₂₀heteroalkyl,C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroarylalkyl, unsubstituted orsubstituted phenyl or naphthyl or unsubstituted or substitutedheteroaryl; or R₂ and R₃, together with the alkylidene carbon atomlinking them, form an unsubstituted or substituted 5-, 6-, 7-, 8- or9-membered ring which may contain further hetero atoms.
 2. A compositionaccording to claim 1 wherein R₁ is —(CH₂)_(k)—N⁺(R₁₀₀R′₁₀₀R″₁₀₀)₃ A⁻,wherein A⁻ is an anion and k is a number from 1 to 4,or is phenylsubstituted with 1 to 5 electron withdrawing substituents selected fromthe group consisting of —O—C(O)OR₁₀₀, —COOR₁₀₀, —C(O)N(R₁₀₀R′₁₀₀),—C(O)—R₁₀₀, —CN, —NO₂, —SO₃R₁₀₀, —CF₃, F, Cl, Br, I, —N(R₁₀₀,R′₁₀₀R″₁₀₀)₃ ⁺A⁻, —N(R₁₀₁R′₁₀₁) and

 wherein R₁₀₀, R′₁₀₀ and R″₁₀₀ independently are hydrogen, unsubstitutedor substituted C₁-C₁₈alkyl or phenyl or two of R₁₀₀, R′₁₀₀andR″₁₀₀together with the nitrogen atom to which they are bonded form a 5or 6 membered-ring which may contain a further nitrogen atom; * is thepoint of attachment and A⁻ is an anion, R₁₀₁ and R′₁₀₁ independently are—C(O)—R₁₀₀, —C(O)N(R₁₀₀R′₁₀₀) or —C(O)OR₁₀₀; or R₁ together with theelectron withdrawing substituent is a group


3. A composition according to claim 1 wherein R₁ is—(CH₂)_(k)—N⁺(R₁₀₀R′₁₀₀R″₁₀₀)₃ A^(−, wherein A) ⁻ is an anion and k is anumber from 1 to 4 or is phenyl substituted with 1 to 5 electronwithdrawing substituents-which are —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A⁻, whereinR₁₀₀, R′₁₀₀ and R″₁₀₀ are independently hydrogen, C₁-C₁₈alkyl or phenyl,or two of R₁₀₀, R′₁₀₀ and R″₁₀₀ together with the nitrogen atom to whichthey are bonded form a 5 or 6 membered-ring which may contain a furthernitrogen atom, or R₁ together with the electron withdrawing substituentis a group

wherein * is the point of attachment and A⁻ is an anion.
 4. Acomposition according to claim 1 wherein formula (2) has the structure

wherein R₁ is phenyl substituted with 1 to 5 electron withdrawingsubstituents —N(R₁₀₀R′₁₀₀ R″₁₀₀)₃ ⁺A⁻ wherein the R₁₀₀, R′₁₀₀, R″₁₀₀independently are hydrogen, C₁-C₁₈alkyl or phenyl, or two of R₁₀₀,R′₁₀₀, R″₁₀₀together with the nitrogen atom to which they are bondedform a 5 or 6 membered-ring which may contain a further nitrogen atom;and A⁻ is an anion, or R₁ together with the electron withdrawingsubstituent is a group

and * is the point of attachment; R₂ denotes hydrogen, unsubstituted orsubstituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl,C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl, C₃-C₂₀heteroalkyl,C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroaralkyl, unsubstituted orsubstituted aryl, or unsubstituted or substituted heteroaryl; R₅,R₆,R₇and R₈ independently from each other are hydrogen, unsubstituted orsubstituted C₁-C₂₈alkyl, C₂-C₂₈alkenyl, C₂-C₂₂alkinyl, C₃-C₁₂cycloalkyl,C₃-C₁₂cycloalkenyl, C₇-C₉aralkyl, C₃-C₂₀heteroalkyl,C₃-C₁₂cycloheteroalkyl, C₅-C₁₆heteroarylalkyl, unsubstituted orsubstituted phenyl or naphthyl; —OR₁₀₀, —NR₁₀₀R′₁₀₀, halogen or a group

 or independently have the meaning as defined for R₁; or R₅ and R₆, R₆and R₇or R₇ and R₈ are linked together to form 1, 2, 3 or 4 carbocyclicor heterocyclic rings, which may be uninterrupted or interrupted by oneor more —O—, —S— or —NR₉— and/or which may be further fused with otheraromatic rings and/or which may be substituted with one or moreC₁-C₆alkyl groups.
 5. The composition according to claim 1, wherein theelectron withdrawing substituents are selected from the group consistingof —O—C(O)OR₁₀₀, —COOR₁₀₀, —C(O)N(R₁₀₀R′₁₀₀), —C(O)—R₁₀₀, —CN, —NO₂,—SO₃R₁₀₀, —CF₃, F, Cl, Br, I, —N(R₁₀₀R′₁₀₀R″₁₀₀)₃ ⁺A−, —N(R₁₀₁R′₁₀₁) and

 wherein R₁₀₀, R′₁₀₀ and R″₁₀₀ independently are hydrogen, unsubstitutedor substituted C₁-C₁₈alkyl or phenyl or two of R₁₀₀, R′₁₀₀ and R″₁₀₀together with the nitrogen atom to which they are bonded form a 5 or 6membered-ring which may contain a further nitrogen atom; * is the pointof attachment and A⁻ is an anion, R₁₀₁ and R′₁₀₁ independently are—C(O)—R₁₀₀, —C(O)N(R₁₀₀R′₁₀₀) or —C(O)OR₁₀₀; or R₁ together with theelectron withdrawing substituent is a group

where * is the point of attachment.